Louisiana State University
LSU Digital Commons
LSU Historical Dissertations and Theses
Graduate School
1973
The Single-Crystal X-Ray-Diffraction Study of
Selected Organic and Inorganic Molecules.
Michael Ernest Witt
Louisiana State University and Agricultural & Mechanical College
Follow this and additional works at: http://digitalcommons.lsu.edu/gradschool_disstheses
Recommended Citation
Witt, Michael Ernest, "The Single-Crystal X-Ray-Diffraction Study of Selected Organic and Inorganic Molecules." (1973). LSU
Historical Dissertations and Theses. 2584.
http://digitalcommons.lsu.edu/gradschool_disstheses/2584
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X erox U niversity M icrofilm s
3D0 N orth Z ee b R oad
Ann A rbor, M ichigan 46106
1
I
74-18,380
WITT, Michael Ernest, 1947THE SINGLE CRYSTAL X-RAY DIFFRACTION STUDY
OF SELECTED ORGANIC AND INORGANIC MOLECULES.
The Louisiana State University and Agricultural
and Mechanical College, Ph.D., 1973
Chemistry, inorganic
: U niversity Microfilms, A XEROX C om pany, A nn Arbor, M ichigan
TH IS D ISSERTATION HAS BEEN M ICROFILM ED EXACTLY AS RECEIVED.
THE SINGLE CRYSTAL X-RAY DIFFRACTION
STUDY OF SELECTED ORGANIC AND
INORGANIC MOLECULES
A D is s e rta tio n
S u b m itted t o th e G ra d u ate F a c u lty o f th e
L o u is ia n a S ta te U n iv e r s i ty and
A g r i c u l t u r a l and M ec h a n ica l C o lle g e
i n p a r t i a l f u l f i l l m e n t o f th e
r e q u ire m e n ts f o r th e d e g re e o f
D o c to r o f P h ilo s o p h y
in
The D ep artm en t o f C h em istry
by
M ic h a e l E r n e s t W itt
B. S ., U n i v e r s ity o f F l o r i d a , 1969
D ecem ber, 1973
To my l o v in g w i f e , J u d i .
ii
ACKNOWLEDGEMENT
The a u th o r w is h e s t o e x te n d h i s s i n c e r e g r a t i t u d e t o
P r o f e s s o r S. F . W atk in s who h a s b e en th e so u rc e o f I n s p i r a t i o n
and g u id a n c e i n th e c o m p le tio n o f t h i s w ork.
H is le n g th y d i s ­
c u s s io n s and p e r s o n a l f r i e n d s h i p h av e made th e a c h ie v e m e n t o f
t h i s g o al p o s s ib le .
Thanks i s a l s o due t o th e members o f th e a u t h o r 's
r e s e a r c h gro u p who s p e n t many h o u rs d i s c u s s in g p ro b lem s and
id e a s t h a t a r o s e i n th e s e s t r u c t u r a l d e te r m in a tio n s .
The s k i l l and e f f i c i e n c y o f th e t y p i s t , Ms. Suzann
F i n l e y , i s m ost d e e p ly a p p r e c i a t e d .
L a s t, b u t n o t l e a s t , th e a u th o r w ould l i k e t o th a n k h i s
p a r e n t s and lo v in g w if e Judi whose s u p p o rt and en co u rag em en t
have made t h i s g o a l c o m p le te .
F i n a n c i a l a s s i s t a n c e i n th e p u b l i c a t i o n o f t h i s D i s s e r ­
t a t i o n was g e n e r o u s ly f u r n is h e d by th e C h a rle s E. C o ates M em orial
Fund o f th e L o u is ia n a S t a t e U n iv e r s i ty d o n a te d by G eorge H. C o a te s ,
and t h i s s u p p o rt i s g r a t e f u l l y ack n o w led g ed .
ill
FOREWORD
M odern c h e m is tr y r e l i e s h e a v i l y on know ledge o f th e
b a s i c s t r u c t u r e o f I n d iv i d u a l m o le c u le s .
By u n d e r s ta n d in g how
atom s a r e bonded t o g e th e r t o form t h e s e l a r g e r a g g r e g a te s , we
n o t o n ly can p r e d i c t f u t u r e r e a c t i o n s b u t a l s o can s y n th e s iz e
s p e c i f i c m o le c u le s to s e r v e s p e c i f i c u s e f u l p u rp o se * .
Many
s p e c tr o c h e m ic a l t o o l s su c h a s I r , nm r, u v , and e s r a r e g e n e r a l l y
u se d to d e te rm in e q u a l i t a t i v e l y th e n a tu r e o f b o n d in g .
However,
by u se o f s i n g l e c r y s t a l X -ra y d i f f r a c t i o n s t u d i e s , we c an make
q u a n t i t a t i v e a s s e s s m e n ts o f th e b o n d in g in t h e s e m o le c u le s .
Bond
l e n g t h s , bond a n g le s , p l a n a r a n g le s , and t o r s i o n a n g le s a r e th e
o b s e r v a t i o n a l d a t a , and w ith c a r e f u l i n t e r p r e t a t i o n o f th e
X -ra y d i f f r a c t i o n r e s u l t s we may u n d e rs ta n d many o f th e s u b t l e
p o i n t s o f b o n d in g th e o r y .
The p u rp o s e o f t h i s s tu d y was t o o b t a i n a c c u r a te bond
l e n g th s and a n g le s f o r t h r e e s e l e c t e d compounds and to e x p la i n
th e b o n d in g d is p la y e d i n th e s e m o le c u le s .
The f i r s t two m o le c u le s
a r e t r a n s i t i o n m e ta l co m p lex es, [Pd(FU M N )(PPh^)^!
[ir(TC M ) (CO) ( P F h ^ g ] • % C6H6*
and
M o lec u le s s i m i l a r t o th e s e a r e
u se d i n hom ogeneous c a t a l y s i s and in o r d e r t o r a t i o n a l i z e a
m echanism f o r th e s e c a t a l y t i c r e a c t i o n s , know ledge o f th e
iv
m o le c u la r s t r u c t u r e s o f th e c a t a l y s t and i t s
s e n tia l.
in t e r m e d i a t e s i s e s ­
The t h i r d compound s t u d i e d i s th e o r g a n ic n a t u r a l p r o d u c t,
T a m a u lip ln -A , i s o l a t e d fro m c e r t a i n p o p u la ti o n s o f th e p l a n t s p e c ie s
A m brosia c o n f e r t i f l o r a DC.
Compounds o f t h i s ty p e hav e b e en found
t o d i s p l a y a n tile u k e m i c and t u m o r - i n h i b i t o r y c a p a b i l i t i e s , and
know ledge o f t h e i r s t r u c t u r e s w i l l be e s s e n t i a l t o t h e u n d e r s ta n d in g
o f why c e r t a i n o f t h e s e compounds d i s p l a y t h i s c a p a b i l i t y and o t h e r s
do n o t .
T h e r e f o r e , i n th e f o ll o w in g t e x t , th e r e s u l t s f o r th e s e
t h r e e X .-ra y d i f f r a c t i o n s t u d i e s w i l l be p r e s e n t e d , and a n e x p l a n a t i o n
o f o b s e rv e d b o n d in g w i l l be d i s c u s s e d .
v
TABLE QF CONTENTS
Page
*
A cknow ledgem ent...........................................................................
m
F o rew o rd ................................... .........................................................................
iv
L i s t o f T a b le s ........................................................................................................
v iii
L i s t o f F i g u r e s .....................................................................................................
x
A b s t r a c t . . . , ............................................................................................................
x ii
C h a p te r
S t r u c t u r e o f [PdCFU M N H PPh^^l.....................................
1
I n t r o d u c t i o n ............................................................................
2
C r y s t a l D a ta ............................................................................
4
E x p e rim e n ta l P r o c e d u re ......................................................
6
X.
S o lu t io n o f th e S t r u c t u r e
C h a p te r
II.
..........................
11
D is c u s s io n ................................................
41
R e f e r e n c e s ..................................................
59
S t r u c t u r e o f [ir(TC M ) (CO) ( P P h ^ ^ l ' % ^6**6‘ ’ * *
I n t r o d u c t i o n .............................................................................
63
C r y s t a l D a ta ............................................................................
66
E x p e rim e n ta l P r o c e d u r e ......................................................
68
S o lu t io n o f th e S t r u c t u r e ...............................................
73
D is c u s s io n ................................................................................. 113
R e f e r e n c e s ....................................................................................136
C h a p te r
I I I . S t r u c t u r e o f T a m a u lip in -A ................................................... 139
I n t r o d u c t i o n ..................................................................
vi
140
Page
C r y s ta l D a ta ....................................................
142
E x p e rim e n ta l P ro c e d u re .....................................................
144
S o lu tio n o f th e S t r u c t u r e . . ............................................
146
D is c u s s io n ....................................
163
R e f e r e n c e s .................................................................................
170
V i t a ..............................
1...................
v ll
172
LIST OF TABLES
T able
I.
Page
A tom ic C o o rd in a te s And T herm al P a ra m e te rs
F o r [Pd(FUMN)(PFh3) 2 ] ............................................................
II.
E u l e r l a n R o ta tio n AngleB F o r The R ig id G roups
In [Pd(FUMN)(PPh3 ) 2 ] .......................................................
III.
CfiH6 ..............................................
80
E u l e r i a n R o t a t i o n a l A n g les F o r The R ig id
G roups I n [ir(TC M ) (CO) ( P P h ^ ] • % CgHg...................
X.
57
A tom ic C o o rd in a te s And T herm al P a ra m e te rs F o r
[lr(T C M )(C O )(P Ph3) 2 ] ^
IX.
51
A Summary o f C y a n o - S u b s titu te d O le f i n Com plexes
Of P d, P t , and I r ......................................................................
V III.
37
A Summary Of T hree Complexes C o n ta in in g The
FUMN L ig a n d ...................................................................................
V II.
34
L e a s t- S q u a r e s P la n e s D eterm in ed F o r
[Pd(FUMN)(PPh3) 2 ] ......................................................................
V I.
29
Bond L e n g th s And A n g les Found F or
[Pd(FUMN)(PPh3) 2 ] ......................................................................
V.
27
The O bserved And C a lc u la te d S t r u c t u r e F a c to r s
F o r [Pd (FUMN) (PPh3) 2 ] ............................................................
IV.
18
100
The O bserved And C a lc u la te d S t r u c t u r e F a c t o r s
F o r [lr(T C M )(C 0 )(P P h 3 ) 2 ] •h CgHg.....................................
v iii
102
T ab le
X I.
Page
Bond L e n g th s and A n g le s Pound F o r The
D is o rd e re d and A n i s o t r o p i c M odels o f
[lr(T C M )(C 0 )(P P h 3 ) ^ • h C6H6- .............................................
X II.
L e a s t- S q u a r e s P la n e s D eterm in ed
F o r [lr(T C M )(C O )(P P h 3) 2 ]
X III.
10fr‘
•h CgHg....................................
A tom ic C o o r d in a te s and T h erm al P a r a m a te r s
109
For
T a m a u lip in -A , Cl 5H2 q° 3 ...........................................................
XIV.
The O b serv ed and C a l c u l a t e d S t r u c t u r e F a c t o r s
F o r T a m a u lip in -A ,
XV.
...............................................
156
Bond L e n g th s and A n g le s Found F o r
T a m a u lip in -A , Cj^H 2 q0 3 .............................................................. 158
XVI.
T o r s io n A n g le s Found F o r
T a m a u lip in -A ,
161
ix
LIST OF FIGURES
F ig u r e
1.
Page
The M o le c u la r C o n f ig u r a t io n o f
[Pd(FUMN)(PFh3 ) 2 ] .........................................................................
2.
C u s a c h 's M odel o f B onding F o r O l e f i n i c C om plexes
o f T r a n s i t i o n M e t a ls ...................................................................
3.
16
E n e r g ie s F o r The H ig h e s t O ccu p ied
45
TT M o le c u la r
O r b i t a l and Low est Empty TT A n tib o n d in g O r b i t a l
Of S e v e r a l O l e f i n s .......................................................................
4.
The M o le c u la r C o n f ig u r a tio n Of
[lrC TC M )(C O )(PPh3 ) 2 3 * % C6H6 ...............................................
5.
End On View Of The D is o r d e r e d And
A Summary Of Bond L e n g th s
114
I s o t r o p i c M odels
F o r [lr(T C M )(C O )(P P h 3 ) 2 ] • k CgHg......................................
6.
48
118
AndA n g le s D is p la y e d I n
The D is o rd e re d And A n i s o t r o p i c M odels o f
[lr(T C M )(C O )(P P h 3 ) 2 ] • % CgHg...............................................
7.
A P a c k in g D iagram Of M o le c u le s
For
[lr(T C M )(C O )(P P h 3) 2 ] * h CgHg...............................................
8.
127
I n f r a r e d S p e c tru m F o r
c is -[lr(T C M )(C O )(F P h 3 ) 2 ] ...........................................................
9.
120
130
I n f r a r e d S p e c tru m F o r
tra n s -[lr(T C M )(C O )(P P h 3 ) 2 ]
x
........................................
133
F ig u r e
10.
Page
The M o le c u la r C o n f ig u r a tio n o f T a m a u lip in -A ,
C15H2 0 °3 .............................................................................................
11.
A C om parison Of The S k e l e t a l R ing S t r u c t u r e s Of
M elam podin (^21^24^9^
^ amau^^P^n“^ ^ 1 5 ^ 2 0 ^ 3 ^
xi
164
ABSTRACT
The m o le c u la r s t r u c t u r e o f f u m a r o n l t r l l e b i s ( t r i p h e n y l p h o s p h in e ) p a lla d iu r a ( 0 ) ,
[PdCCNHCCHClOCPPhg^li h a s b e e n d e te rm in e d
by X - r a y d i f f r a c t i o n a n a l y s i s u s in g Mo K a r a d i a t i o n .
The p a le
y e llo w compound c r y s t a l l i z e s i n t h e m o n o c lin ic s p a c e g ro u p P 2 /n
w i t h f o u r m o le c u le s p e r u n i t c e l l .
The u n i t c e l l c h o se n h a s
d im e n s io n s a, = 2 0 .2 7 8 ( 1 ) , b = 9 .3 0 3 2 ( 1 ) , c = 2 1 .1 5 3 (1 ) X,
P = 1 1 7 .8 9 ( 1 ) ° , V = 3527 X3 , and FQ00 » 1448 e l e c t r o n s .
o b s e rv e d and c a l c u l a t e d d e n s i t i e s a r e 1 .3 3 and 1 .3 4 g.cm
The
-3
C o u n te r m eth o d s w ere u sed i n th e c o l l e c t i o n o f 3057 r e f l e c t i o n s
w hose n e t i n t e n s i t i e s w e re g r e a t e r t h a n t h r e e tim e s t h e i r
e s ti m a te d s ta n d a r d d e v i a t i o n s .
The s t r u c t u r e h a s b e e n r e f i n e d
b y l e a s t - s q u a r e s m eth o d s t o R = 0 .0 6 8 and wR = 0 .0 5 0 w ith a l l
p h e n y l r i n g s t r e a t e d a s r i g i d g ro u p s .
E ach o f th e f o u r m o le c u le s
i n th e u n i t c e l l c o n ta i n s a c r y s t a l l o g r a p h i c tw o - f o ld a x i s .
T h e r e f o r e , tw o h a l f - m o l e c u l e s w e re in v o lv e d i n th e a sy m m e tric
u n i t , b u t bond l e n g t h s and a n g le s i n e a c h - h a l f do n o t d i f f e r
s ig n ific a n tly .
The m o le c u le e x h i b i t s a p l a n a r c o n f i g u r a t i o n
w i t h th e p a lla d iu m , p h o s p h o ru s ,
d e f i n i n g th e m o le c u la r p la n e .
o rd in a tio n sp h ere a r e :
and two e th y le n e c a rb o n ato m s
Bond l e n g t h s i n th e f i r s t co­
P d -P , 2 .3 3 3 ( 1 ) ; Pd-C , 2 .1 1 4 ( 6 ) ;
x ii
C e C, 1 .4 4 8 ( 7 ) X.
S in g le c r y s t a l X -ra y d i f f r a c t i o n a n a l y s i s h a s been
p e rfo rm ed on tric y a n o m e th a n id o -N -c a rb o n y l b i s ( tr ip h e n y l p h o s p h in e ) ir i d iu m ( I ) .
The y e llo w c r y s t a l s o f
[irC C C C lO ^H C O K P P h g ^] • % ^6^6 w^ i c h become am orphous on
s ta n d in g due t o l o s s o f b en zen e m o le c u le s from th e l a t t i c e ,
c r y s t a l l i z e i n th e t r l c l l n i c sp a c e gro u p P I w ith two fo rm u la
u n its p e r u n it c e ll .
The u n i t c e l l c h o se n had d im e n sio n s a =
1 1 .6 1 5 (9 ) b = 1 2 .5 6 2 ( 9 ) , c = 16 .9 7 6 (1 2 ) X, * = 9 1 .2 4 ( 7 ) ,
8 = 9 9 .4 6 ( 5 ) , y = 114.91 ( 6 ) ° , V = 2204 X3, and FQ00 = 866
_3
e l e c t r o n s . The c a l c u l a t e d d e n s i t y i s 1 .3 2 g.cm . 2386 m e a su r­
a b le i n t e n s i t i e s w ere c o l l e c t e d w ith Mo K a r a d i a t i o n by c o u n te r
m ethods and used in th e l e a s t - s q u a r e s r e fin e m e n t t o p ro d u ce two
e q u a ll y v a l i d m odels w ith w e ig h te d r e s i d u a l f a c t o r s 0 .0 5 1 and
0 .0 5 0 .
One cyano g ro u p o f th e N-bonded tric y a n o m e th a n id e io n
(TCM) a p p e a rs e i t h e r t o be d is o r d e r e d o r t o d i s p l a y a b n o rm a lly
la r g e v i b r a t i o n a l m o tio n , b o th m odels a r e c o n s i s t e n t w ith a n o n p la n a r TCM.
The c o o r d in a ti o n g eo m etry a b o u t Xr i s t r a n a p l a n a r ;
th e mean TCM p la n e i s t i l t e d
c a . 21° w i t h r e s p e c t t o t h i s p la n e .
The I r - N (TCM) bond le n g th i s 1 .9 9 (1 ) X, th e mean X r-P d i s t a n c e
i s 2 .3 3 0 (9 ) X and th e I r -C (CO) d i s t a n c e i s 1 , 7 2 ( 2 ) X.
The m o le c u la r s t r u c t u r e o f T a m a u lip in -A ,
a s e s q u ite r p e n e l a c t o n e , h a s b een d e te rm in e d by s i n g l e c r y s t a l
X -ra y d i f f r a c t i o n a n a l y s i s u s in g Mo K a r a d i a t i o n .
The compound
c r y s t a l l i z e s in th e o rth o rh o m b ic sp ace group P 2 ^ 2 j2 ^ w ith f o u r
x iii
m o le c u le s p e r u n i t c e l l .
The c e l l c o n s ta n ts a r e a, = 7 .8 9 0 ( 9 ) ,
b = 11.957 ( 1 3 ) , c * 1 4 .6 4 9 (1 7 ) 8 , V = 1382 8 3 , and F00Q = 536
e le c tro n s .
1 .1 9 g.cm
-3
The o b se rv e d and c a l c u l a t e d d e n s i t i e s a r e 1 .2 0 and
re s p e c tiv e ly .
C o u n te r m ethods w ere used i n th e
m easurem ent o f 733 r e f l e c t i o n s whose n e t i n t e n s i t i e s a r e g r e a t e r
th a n two tim e s t h e i r e s tim a te d s ta n d a r d d e v i a t i o n s .
D ir e c t p h a s in g
m ethods w ere used i n th e s o l u t i o n and f u l l m a tr ix l e a s t - s q u a r e s
r e fin e m e n t in c lu d in g h y d ro g e n atom s le d to a c o n v e n tio n a l R
f a c t o r o f 0 .0 4 0 .
The two m e th y l g ro u p s a tta c h e d t o th e te n
membered r i n g a r e in th e syn c o n f ig u r a t io n w ith th e 1 ,5 d o u b le
bonds b o th t r a n s .
x iv
CHAPTER I .
THE X-RAY STRUCTURE DETERMINATION
OF
FUMARONITRILEBISTRIPHENYLPHOSPHINE PALLADIUM (0 )
[Pd(FUMN)(PPh3) 2 ]
1
INTRODUCTION
In 1827 th e D an ish p h a r m a c is t, W. C. Z e is e , c h a r a c t e r i z e d
a compound w hose s to ic h io m e t r y was PtClg* ^ 2 H4*
1
t h i s compound, h e I s o l a t e d th e s a l t , K [PtC l^C 2 H ^].
a<^ i t i o n to
F o r a p e r io d o f
127 y e a r s , th e s t r u c t u r e o f t h e s a l t re m a in ed unknown; th e n , i n
1954, th e c r y s t a l s t r u c t u r e was d e te rm in e d by X -ray d i f f r a c t i o n .
2
Z e i s e 's s a l t , a s i t i s now known, was th e b e g in n in g o f a new e ra
f o r i n o r g a n ic c h e m is ts ; and th e f i e l d o f O rg a n o m e ta llic c h e m is tr y
h a s s in c e grown t o immense p r o p o r t i o n s .
C o u n tle s s c o m b in a tio n s
o f t r a n s i t i o n m e ta ls and o r g a n ic lig a n d s have r e s u l t e d i n th e
s y n th e s e s o f num erous m o le c u le s .
I n o r d e r t o r a t i o n a l i z e th e way i n w hich m e ta ls and
o r g a n ic l ig a n d s a r e bound t o g e t h e r , in f o r m a tio n p e r t a i n i n g t o th e
p h y s i c a l and e l e c t r o n i c c h a r a c t e r i s t i c s o f o r g a n o m e ta llic compounds
m ust be o b ta in e d .
i r , nmr, uv, and o t h e r p h y s i c a l m easurem ents
c e r t a i n l y p ro v id e u s w i t h in f o r m a tio n a b o u t m o le c u le s and t h e i r
p ro p e rtie s .
However, i n o r d e r t o make e x te n s iv e g e n e r a l i z a t i o n s
and r a t i o n a l i z a t i o n s a b o u t t h e s e m o le c u le s , th e bond l e n g t h s ,
bond a n g le s , t o r s i o n a n g le s , and d i h e d r a l a n g le s a r e needed t o
c o m p lete th e s t r u c t u r a l p i c t u r e .
C om plete d a t a o f t h i s s o r t a re
d i f f i c u l t t o o b t a i n f o r e v e ry o r g a n o m e ta llic compound by means o f
2
3
X -ray d i f f r a c t i o n b e c a u s e o f th e c o s t and c o m p le x ity o f t h e
m eth o d s in v o lv e d .
W. H. B a d d le y and h i s c o -w o rk e rs a t L o u is ia n a S t a t e U ni­
v e r s i t y , B ato n R ouge, hav e le d r e s e a r c h g ro u p s aro u n d th e w o rld i n
p r e p a r i n g o r g a n o m e ta l lic compounds c o n t a i n i n g c y a n o - s u b s t i t u t e d
a c e t y l e n e and e th y le n e m o le c u le s bonded t o Group V I I I m e t a l s .
3-9
O nly a s m a ll number o f t h e s e compounds hav e b e e n a n a ly z e d by X -ra y
d i f f r a c t i o n te c h n iq u e s t o d e te r m in e th e m o le c u la r s t r u c t u r e s . ^ ^
To v e r i f y th e c u r r e n t t h e o r i e s o f b o n d in g i n t h e s e u n iq u e
m o le c u le s , t h e c r y s t a l s t r u c t u r e o f one member o f t h i s cy an o s e r i e s
w as u n d e r ta k e n .
The compound a n a ly z e d w as f u m a r o n i t r i l e b i s ( t r i -
p h e n y lp h o s p h in e ) p a lla d iu m ,
Pd(FUMN)(PPh3) 2 (w h ere f u m a r o n i t r i l e ,
FUMN = t r a n s 1 , 2 - d i c y a n o e t h y l e n e ; Ph = p h e n y l g r o u p ) .
The s t r u c t u r e
o f th e p la tin u m a n a lo g , Pt(FUM N)(PPh3) 2 ^ a s ^ eeri d e te r m in e d ,
its
10
but
s t r u c t u r e shows i n e x p l i c a b l e d e v i a t i o n s fro m th e t r e n d s ob­
s e r v e d i n th e o t h e r t h r e e members o f t h i s s e r i e s , Ir(H)(CO)(FUM N)
(P P h3) 2 , n
Ir(B r)(C O )(T C N E )(F P h 3) 2 , 12 and P t ( T C N E ) ( P P h ^ . 15
T h e r e f o r e , t h e c r y s t a l s t r u c t u r e a n a l y s i s o f Pd(FUMN)(PPh3) 2 was
i n i t i a t e d f o r two r e a s o n s .
The f i r s t r e a s o n t h i s s t r u c t u r e w a s '
u n d e r ta k e n w as t o com pare t h e bond l e n g t h s and a n g le s w i t h th o s e
o b ta in e d f o r th e p la tin u m a n a lo g w hose r e s u l t s a p p e a r i n a c c u r a t e ;
t h e seco n d r e a s o n w as t o add p e r t i n e n t d a t a t o th e s e r i e s o f
cy an o s u b s t i t u t e d compounds i n o r d e r t o s u b s t a n t i a t e th e p ro p o s e d
m ethod o f b o n d in g .
35
CRYSTAL DATA
The p a le y e llo w , m o n o c lin ic c r y s t a l o f Pd(FUMN)(PPh^)
^ 4 0 ^ 32 ^ 2 ^ 2 ^ *
t h a t was u sed i n th e d a t a c o l l e c t i o n m easu red a p ­
p r o x im a te ly 0 .3 0 x 0 .3 2 x 0 .3 0 mm.
The c r y s t a l was m ounted a lo n g
t h e c r y s t a l l o g r a p h i c b a x i s and had e i g h t w e l l - d e f i n e d f a c e s b e ­
lo n g in g t o th e { l0 0 } , (O lO ), { 0 0 l} , [ l O l ) , and {101} fo rm s.
W ith
su c h w e ll- d e f in e d f a c e s , o p t i c a l a lig n m e n t was e a s i l y a c c o m p lis h e d .
The m o n o c lin ic u n i t c e l l h a s d im e n sio n s a = 2 0 .2 7 8 ( 1 ) , b = 9 .3 0 3 2
( 1 ) , _c = 2 1 .1 5 5 (1 ) X, 0 = 1 1 7 .8 9 ( 1 ) ° ( th e num bers i n p a r e n th e s e s
d e n o te th e e r r o r s i n th e l a s t s i g n i f i c a n t f i g u r e s ) , V ■= 3527 X^,
and Fqqq = 1448 e l e c t r o n s .
The o b se rv e d d e n s i t y , d e te rm in e d b y
t h e f l o t a t i o n te c h n iq u e u s in g a n aq u eo u s s o l u t i o n o f
i s 1 .3 3 g.cm
-3
le a d n i t r a t e ,
.
The c a l c u l a t e d d e n s i t y w ith f o u r m o le c u le s p e r
_3
u n i t c e l l i s 1 .3 4 g.cm . Even th o u g h th e c r y s t a l had s e v e r a l
w e ll-fo rm e d f a c e s , i t s o v e r a l l sh ap e w as i r r e g u l a r .
The c r y s t a l
w as o r i g i n a l l y c le a v e d fro m a l a r g e r c r y s t a l and th e d im e n s io n o f
th e sp ecim en i n th e [0 1 0 "] d i r e c t i o n v a r i e d from 0 .1 6 0 t o 0 .3 2 0 mm.
C a l c u la tio n o f th e l i n e a r a b s o r p tio n c o e f f i c i e n t , |jb, was d e te rm in e d
t o be 6 .3 9 cm
C o n s id e rin g th e c r y s t a l t o b e a cube w hose ed g es
a r e 0 .3 2 mm., M^max was found t o be 0 .1 8 .
B ecause o f th e i r r e g u l a r
sh ap e o f th e c r y s t a l and b e c a u s e th e v a lu e o f M^max was finia^ i
no
a b s o r p t i o n c o r r e c t i o n was m ade.
The o n ly s y s te m a tic a b s e n c e s e x t r a c t e d from e m u lsio n
f ilm s w ere h 0 £ , h +
Jfc
= 2n + 1.
Two sp ac e g ro u p s a r e c o n s i s t e n t
w ith th e s e a b s e n c e s , i . e . , th e c e n tr o s y n m e tr lc P 2 /n
13)
39
2
39
and th e n o n -c e n tro s y m m e tric Pn (G , number 7 ) .
number
S in c e
th e fo rm e r c o n ta i n s a c e n t e r o f sym m etry, p r e lim in a r y s o l u t i o n
o f th e s t r u c t u r e was a cc o m p lish e d u s in g t h i s sp a c e g ro u p .
On
c o m p le tio n o f th e s t r u c t u r e , b o th p o s s i b l e s p a c e g ro u p s w ere
t e s t e d and i t was found t h a t th e m ost l i k e l y sp a c e g ro u p i s th e
c e n tro s y m m e tric , P 2 /n .
EXPERIMENTAL PROCEDURE
The o r i e n t a t i o n and l a t t i c e p a ra m e te rs o f t h e m o n o c lin ic
c r y s t a l w ere o b ta in e d by a s e r i e s o f f i l m e x p o s u re s u s in g Ni
f i l t e r e d Cu K 0£ r a d i a t i o n (X = 1 .5 4 1 X ) .
P r e c e s s io n and e q u i i n -
c l i n a t i o n W e isse n b e rg cam era te c h n iq u e s w ere used t o d e te rm in e
th e o r i e n t a t i o n o f th e c r y s t a l s .
F o u r c r y s t a l s w ere o r ie n te d
i n t h i s w ay s in c e th e p h o to g ra p h s o f th e f i r s t t h r e e in d ic a te d
t h a t th e y w ere e i t h e r tw in n ed o r th e y c o n ta in e d s a t e l l i t e c r y s t a l s
w h ich made them u n s u i t a b l e f o r s i n g l e c r y s t a l d i f f r a c t i o n w ork.
The d i f f r a c t i o n p a t t e r n s d is p la y e d on e m u lsio n f i l m s by th e f o u r t h
c r y s t a l w ere th e n in d ex ed and th e s y s te m a tic a b s e n s e s w ere d e t e r ­
m in ed .
T h is c r y s t a l was ju d g e d t o be a good s i n g l e c r y s t a l and
i t w as, t h e r e f o r e , t r a n s f e r e d t o th e E n ra f-N o n iu s PAD-3 d i f f r a c t o ­
m e te r i n p r e p a r a t i o n f o r d a ta c o l l e c t i o n .
B e fo re a lig n m e n t and c e n t e r i n g p ro c e d u re s co u ld b e
u n d e r ta k e n , th e n u l l v a lu e s f o r th e f o u r d i f f r a c t o m e t e r a n g l e s ,
t h e t a , p h i , c h i , and omega, had t o b e d e te r m in e d .
37
The v a lu e
o f t h e t a was d e te rm in e d when th e X -ra y tu b e was i n i t i a l l y a l ig n e d .
T h is was done by re d u c in g th e power on th e X -ra y tu b e t o 20 kV
and 4mA, rem oving th e beam s t o p , and d i r e c t i n g th e beam i n t o th e
d e t e c t o r w hose s u r f a c e was c o v ered w ith a t h i n le a d f o i l t o
a t t e n u a t e th e im p in g in g r a d i a t i o n and p r e v e n t damage t o th e
d e te c to r.
The number o f c o u n ts was m axim ized by c h a n g in g t h e t h e t a
g e a r d r iv e m a n u a lly .
The t h e t a v a lu e d i s p l a y i n g th e maximum number
o f c o u n ts w as th e i n i t i a l n u l l t h e t a v a l u e .
T h is v a lu e o f th e t a
i s th e s e t t i n g a t w h ic h th e beam p a s s e s a p p ro x im a te ly th ro u g h th e
c e n t e r o f th e d e t e c t o r .
S in c e p h i i s a llo w e d t o r o t a t e th ro u g h
3 6 0 °, th e n u l l v a lu e f o r t h i s a n g le i s m e a n in g le s s andt t h e r e f o r e ,
w as s e t t o z e r o .
To d e te r m in e th e n u l l v a lu e s f o r c h i and omega,
th e c r y s t a l had t o be p la c e d on th e d i f f r a c t o m e t e r .
pow er ( 40 kV and 16 mA ) , a r e f l e c t i o n a lo n g t h e b
was o r i e n t e d ro u g h ly f o r d i f f r a c t i o n .
U sin g f u l l
“ft
a x i s (040)
S in c e th e r o t a t i o n
o f th e c r y s t a l was s e t t o c o in c id e w i t h th e b
a x is
a x i s , p h i was
in d e p e n d e n t o f th e r o t a t i o n and was a r b i t r a r i l y s e t t o 0 .0 ° .
The c h i a n g le was s e t t o 9 0 .0 ° .
The a p p ro x im a te t h e t a s e t t i n g
w as o b ta in e d from B r a g g 's e q u a tio n ,
n \ = 2 d ( s i n 9 ),
o
w h e re X = 0 .7 1 0 7 A f o r Mo K 0£ r a d i a t i o n .
Omega was v a r i e d t o
m axim ize th e beam i n t e n s i t y and th e r e f l e c t i o n was c e n te r e d u s in g
t h e to p /b o tto m - l e f t / r i g h t h a lf-m o o n s .
T h is m ethod in v o lv e s
a l t e r n a t e l y b lo c k in g th e to p and b o tto m h a lv e s o f th e d i f f r a c t e d
beam and v a r y in g c h i t o g iv e a d e t e c t o r re s p o n s e o f o n e - h a l f th e
p eak maximum f o r e a c h moon.
The t h e t a v a lu e w as v a r i e d i n th e
same way u s in g th e l e f t and r i g h t h a lf-m o o n s .
T h is p r o c e s s o f
c e n t e r i n g was r e p e a te d u n t i l c o n s ta n t v a lu e s f o r t h e t a , c h i , and
omega w ere o b ta in e d and r o t a t i o n a b o u t th e p h i a x i s p ro d u ced no
change i n th e v a lu e o f omega a t maximum p e a k i n t e n s i t y .
The n u l l
v a lu e f o r omega was ta k e n t o b e t h e num ber o b ta in e d i n th e m axim i­
z a t i o n - c e n t e r i n g o f th e (0 4 0 ) r e f l e c t i o n .
The n u l l c h i was c a l c u ­
l a t e d b y s u b t r a c t i n g 90° fro m t h e v a lu e o b ta in e d I n t h e c e n t e r i n g
o f t h e (0 4 0 ) r e f l e c t i o n .
A t t h i s p o i n t , th e f i n e t h e t a n u l l s e t t i n g was d e te rm in e d
b y l o c a t i n g a r e f l e c t i o n (1 0 0 0 ) i n t h e h 0 £ p l a n e .
The r e f l e c t i o n
i n t e n s i t y was m axim ized by th e to p /b o tto m c e n t e r i n g te c h n iq u e d e s ­
c rib e d .
Once c e n t e r e d , t h e F r i e d e l tw in (1 0 0 0 ) w as a l s o c e n te r e d
by c h a n g in g o n ly t h e t a t o n e g a t i v e t h e t a .
W h en 'b o th r e f l e c t i o n s
had b e e n m axim ized i n i n t e n s i t y , th e a v e r a g e o f t h e tw o t h e t a
v h lu e s w as th e t h e t a n u l l ; t h i s w as e q u a l t o 0 .0 0 ° .
T h re e r e f l e c t i o n s , c e n te r e d b y t h e p r e v io u s m eth o d ,
w ere in p u t t o ORIENT**’ and a p a r t i a l l i s t i n g o f t h e g e n e r a l r e ­
f l e c t i o n i n d i c e s , w i t h i n th e s p e c i f i c a t i o n s o f th e m a c h in e , and
t h e i r t h e t a , p h i , and c h i (omega = omega n u l l ) v a l u e s was
g e n e ra te d .
From t h i s l i s t ,
50 r e f l e c t i o n s w ere c a r e f u l l y
c e n te r e d and a l e a s t - s q u a r e s d e t e r m i n a t i o n (fro m ORIENT) o f th e
l a t t i c e p a r a m e te r s , o r i e n t a t i o n a n g l e s , and n u l l v a lu e s o f t h e
d i f f r a c t o m e t e r a n g le s was o b t a in e d .
U sin g t h e s e n u l l v a l u e s and l a t t i c e p a r a m e t e r s , a
s e t o f c o n t r o l c a r d s was g e n e r a te d b y DIFSET
d if f r a c tio n d a ta .
16
fo r c o lle c tio n o f
6380 i n t e n s i t y d a t a w e re c o l l e c t e d a u t o m a t i c a l l y
o v e r a p e r io d o f s i x w eeks u s in g Z r f i l t e r e d Mo K O' (X = 0 .7 1 0 7 X)
ra d ia tio n .
The t h e t a / t w o t h e t a s c a n m ethod waa u se d i n t h e c o l -
le c tio n o f in te n s itie s .
17
The s c a n ra n g e w as d e te rm in e d f o r e a c h
r e f l e c t i o n from th e e q u a t i o n ,
A 9 = % ( ACON + BCON (TAN 9 ) ) ,
w h e re ACON and BCON a r e c o n s t a n t s w hose v a lu e s w ere s e t a t 1 .8 0
an d 1 .0 0 .
S u c c e s s iv e a t t e n u a t o r s
w e re a u t o m a t i c a l l y p la c e d i n
t h e beam u n t i l th e c o u n tin g r a t e w as l e s s th a n 2000 c o u n ts p e r
second.
The 20 sec o n d b a ck g ro u n d c o u n ts , c o n d u c te d b e f o r e and
a f t e r e a c h r e f l e c t i o n s c a n , w e re u se d i n DIFDAT^ t o c o r r e c t th e
m e asu re d i n t e n s i t i e s f o r e x tr a n e o u s b ack g ro u n d b y s u b t r a c t i n g
th e a v e r a g e b a c k g ro u n d s fro m th e m easu red i n t e n s i t i e s t o y i e l d
th e n e t i n t e n s i t i e s .
The s ta n d a r d d e v i a t i o n o f th e n e t i n t e n s i t y
was c a l c u l a t e d from t h e e q u a t i o n ,
a ( I ) = ( Cx + ( t ( s c a n ) / ( t fil +
w h ere C^.,
+ CB2} ^
an<* c ^2 a r e t *ie t o t a ^ c ° u n t s » c o u n ts b e f o r e t h e s c a n ,
and c o u n ts a f t e r th e s c a n r e s p e c t i v e l y .
The t ( s c a n ) ,
and t ^
te rm s r e p r e s e n t th e tim e f o r s c a n n in g t h e r e f l e c t i o n and t h e tim e
f o r b a ck g ro u n d c o u n ts b e f o r e and a f t e r t h e r e f l e c t i o n s c a n .
A l o r e n t z and p o l a r i z a t i o n c o r r e c t i o n o f
1 + c o s 2 (2 9 )
Lp = * ' *.........
—
2 s i n (2 6 )
w as a p p l i e d t o th e o b s e rv e d i n t e n s i t i e s .
18
p u nched on c o m p u ter c a r d s f o r f u t u r e u s e .
Reduced d a t a w ere
I n o r d e r t o e n s u r e t h e r e l i a b i l i t y o f th e d a t a , t h r e e
s ta n d a r d r e f l e c t i o n s w e re i n s e r t e d b etw een e v e r y 100 m easu red
re fle c tio n s .
By c o n tin u o u s ly m o n ito r in g th e i n t e n s i t i e s d is p la y e d
b y t h e s ta n d a r d r e f l e c t i o n s , d e t e c t i o n o f c r y s t a l m ovem ent, d e c a y
o f th e c r y s t a l , o r p o s s i b l e m ach in e e r r o r c o u ld b e d e t e c t e d .
The
l a r g e s t d e v i a t i o n o f th e s ta n d a r d i n t e n s i t i e s w as 0.2% w h ic h was
ta k e n a s An i n d i c a t i o n t h a t th e c r y s t a l was v i r t u a l l y s t a t i o n a r y ,
w i t h no d e c a y and no m a lf u n c tio n due t o t h e d i f f r a c t o m e t e r
s y s te m .
11
SOLUTION OF THE STRUCTURE
Of t h e c o m p le te s e t o f 6380 m easu red I n t e n s i t i e s , 3223
w e re o b s e rv e d r e f l e c t i o n s ( I . e . , th o s e w i t h n e t I n t e n s i t y g r e a t e r
th a n 3 <J ( I ) ) .
The o b s e rv e d s t r u c t u r e f a c t o r s , o b ta in e d from
t h e s e d a t a , w e re u se d I n t h e c a l c u l a t i o n o f a P a t t e r s o n i n t e r a to m ic v e c t o r map.
17
S e v e ra l p o s s ib le s o lu tio n s to th e P a tte r s o n
map w e re t r i e d u n s u c c e s s f u l l y b e f o r e p o s i t i o n s o f th e tw o p a lla d iu m
and tw o p h o s p h o ru s
atom s w e re fo u n d w h ic h y i e l d e d a r e s i d u a l
v a l u e (R) o f 0 .2 9 .
The r e s i d u a l f a c t o r , w h ic h m e a s u re s th e
c l o s e n e s s o f f i t o f t h e c a l c u l a t e d and o b s e rv e d s t r u c t u r e f a c t o r s ,
i s d e f in e d a s
R = £
| Fo - F c | / S | Fo | .
Once th e Pd and P ato m s w e re p o s i t i o n e d , t h e EXECXRAY
67 p a ck a g e d c o m p u te r p ro g ram was u se d t o g e n e r a te a F o u r i e r d i f f e r a n c e map, c a l c u l a t i n g ro u g h p h a s e s f o r th e r e f l e c t i o n d a ta
b y u s in g th e p a lla d iu m and p h o sp h o ru s
a to m ic c o o r d i n a t e s .
19
By
c a l c u l a t i n g s e v e r a l s u c c e s s i v e F o u r i e r m aps, u s in g p h a s e s d e r iv e d
fro m p r e v io u s m aps, a d d i t i o n a l ato m s o f t i e
m o le c u le w e re l o c a t e d .
When t h r e e o r m ore c a rb o n s i n a p h e n y l r i n g o f th e tr i p h e n y lp h o s p h in e
20
li g a n d s w ere l o c a t e d , c o m p u te r p ro g ram RBANG
was u se d t o o b t a i n
t h e t h e o r e t i c a l p o s i t i o n s f o r t h e re m a in in g p h e n y l c a r b o n s .
T h is
r i g i d group m ethod in v o lv e s t r e a t i n g th e p h e n y l r i n g a s a r i g i d
r e g u la r hexagon.
A l o c a l o r i g i n , e s t a b l i s h e d on one o f th e c a rb o n s
( u s u a l l y th e c a rb o n bond ed t o th e p h o s p h o r u s ) ,
r i n g w hose G-C bond l e n g t h s w ere a l l 1 .3 9 4 A.
d e f in e d a n I d e a l
”
U sin g t h i s
r i g i d g ro u p and t h e p o s i t i o n s o f known o r s u s p e c te d c a rb o n a to m s,
RBANG c a l c u l a t e d th e c r y s t a l c o o r d i n a t e s f o r th e unknown c a rb o n
atom s a s w e l l a s th e E u l e r ( o r i e n t a t i o n ) a n g l e s f o r th e r i g i d
b o d y .^ ^
A t l e a s t t h r e e o f th e s i x p h e n y l c a rb o n s w ere n eed ed
i n o r d e r t o d e f i n e t h e p la n e i n w h ic h th e r i n g w as p o s i t i o n e d .
By u s in g t h e m ethod o f F o u r i e r s y n t h e s i s i n c o n j u n c t i o n
w ith
th e RBANG r o u t i n e , a l l n o n -h y d ro g e n ato m s w e re l o c a t e d .
H ow ever,
w i t h th e l a r g e num ber o f p o s i t i o n a l and th e r m a l p a r a m e te r s in v o lv e d
i n t h i s m o le c u le , a l e a s t s q u a r e s p ro g ram d e s ig n e d t o t r e a t
p h e n y l r i n g s a s r i g i d g ro u p s was u s e d .
25
T h is p ro g ram , ORFLSD
(O ak R id g e F o r t r a n L e a s t S q u a re s , v e r s i o n D ), w as u sed i n th e f u l l
m a t r i x l e a s t - s q u a r e s r e f in e m e n t o f th e a to m ic p o s i t i o n s and th e rm a l
p a r a m e te r s .
The u s e o f ORFLSD w i t h r i g i d g ro u p r e f in e m e n t re d u c e d
t h e t o t a l num ber o f v a r i a b l e p a r a m e te r s fro m 201 t o 7 9 .
m a t r i x l e a s t - s q u a r e s , m in im iz in g t h e f u n c t i o n 2 w (
F u ll
| Fq | -
j F^ | )^
w as c a r r i e d o u t w i t h w (w e ig h t) = 1 and th e R v a l u e , a f t e r t h r e e
c y c l e s , waB 0 .1 8 .
The r e s i d u a l e l e c t r o n d e n s i t y i n a d i f f e r e n c e s y n t h e s i s
i n d i c a t e d t h a t t h e Pd and P atom s w ere u n d e rg o in g h i g h l y a n i s o t r o p i c
th e r m a l m o tio n .
T h e r e f o r e , a c o r r e c t i o n f o r th e a n i s o t r o p y i n th e
th e r m a l m o tio n o f th e Pd and P ato m s w as c a l c u l a t e d a s ,
T = e x p ( * ( h 2 p 11 + k 2 P2 2 + j&2 P3 3 + 2 (h k P 12 + h £ p 1 3 + kj&P2 3 » ) ,
w h e re h , k , and A a r e t h e i n d i c e s o f r e f l e c t i o n (h k £ ) and t h e
P j j ' s a r e th e a n i s o t r o p i c th e rm a l f a c t o r s .
S in c e th e p a lla d iu m
o c c u p ie s a s i t e o f tw o - f o ld c r y s t a l l o g r a p h i c sym m etry ( 2 e and 2 f ,
num ber 1 3 ) ,
39
th e th e r m a l p a r a m e te r s p ^2 and P 23 a r e I n v a r i a n t
and i d e n t i c a l l y z e r o .
A t t h i s p o i n t , a s im p le w e ig h tin g schem e w as a p p l i e d
i n th e fo rm o f
w = 1 / ( s i g Yo) 2 ,
w h e re ( s i g Yq) i s th e s ta n d a r d d e v i a t i o n o f th e o b s e rv e d s t r u c t u r e
f a c t o r d e f in e d a s ,
s i g Yq = s ig (X ) / 2 .0 ( Lp *
W ith th e a d d i t i o n o f t h e w e ig h tin g scheme and t h e im proved th e rm a l
m o d e l, c l o s e r a g re e m e n t b e tw ee n t h e o b s e rv e d and c a l c u l a t e d
s t r u c t u r e f a c t o r s , a f t e r t h r e e c y c le s o f l e a s t - s q u a r e s , was r e ­
f l e c t e d i n th e r e s i d u a l v a lu e s R = 0 .0 9 0 and R^ = 0 .0 8 6 , w h e re R^
i s th e w e ig h te d r e s i d u a l f a c t o r ,
= ( 2 w( I Fo | -
| Fc | ) 2 / E »
| F0 | 2 ) *.
S in c e t h e r e w e re t h i r t y h y d ro g e n atom s d i s t r i b u t e d among
th e s i x t r i p h e n y lp h o s p h in e g ro u p s , c a l c u l a t e d p o s i t i o n s f o r th e s e
ato m s a ssu m in g a C-H bond l e n g t h o f 1 .0 0 £ , w e re s u b m itte d w i th
t h e o t h e r a to m ic c o o r d i n a t e s t o ORFLSD.
The l e a s t - s q u a r e s c y c le s
p ro d u c e d r e s i d u a l f a c t o r s o f R = 0 .0 8 0 and Rw ■= 0 .0 6 2 .
Up t o t h i s
p o i n t , r e fin e m e n t had h e ld a l l p h en y l c a rb o n te m p e ra tu re f a c t o r s
e q u iv a le n t.
T hree a d d i t i o n a l c y c le s o f ORFLSD w ere com puted
v a r y in g in d i v i d u a l i s o t r o p i c te m p e ra tu re f a c t o r s o f th e r i n g c a r ­
bons t o g iv e R = 0 .0 6 7 and R^, = 0 .0 5 3 .
Once th e l e a s t - s q u a r e s p r o c e s s was c o m p le te d , th e d a ta
w ere re v ie w e d and 83 r e f l e c t i o n s w ere fo u n d t o be re d u n d a n t and
78 w ere n o t w e ll r e c o r d e d .
T hese 166 r e f l e c t i o n s w ere removed from
th e d a ta s e t le a v in g 3057 r e f l e c t i o n s .
A f t e r two a d d i t i o n a l
c y c le s o f ORFLSD, th e f i n a l r e s i d u a l v a lu e s w ere R = 0 .0 6 8 and
R = 0 .0 5 0 w ith a n e r r o r o f f i t (ERF) = 2 .8 2 2 5 w here
w
ERF = S w (
| F
o
| -
| F
c
| ) 2 / (3057 - 1 2 5 ).
The above s o l u t i o n and re f in e m e n t o f th e s t r u c t u r e w ere
c a r r i e d o u t i n th e c e n tro s y m m e tric sp a c e g ro u p , F 2 /n .
However, th e
n o n -c e n tro s y m m e tric sp ace g ro u p , Pn, i s a l s o c o n s i s t e n t w ith th e
d if f r a c tio n d a ta .
The in v e r s i o n c e n te r and tw o -f o ld symmetry
c o n s t r a i n t s w ere rem oved, th e atom f r a c t i o n a l c o o r d in a te s w ere
s h i f t e d a t random by 0 .0 0 1 t o 0 .0 0 5 fro m t h e i r r e f i n e d p o s i t i o n s
t o p r e v e n t fo r m a tio n o f a s i n g u l a r m a tr i x , and th e f u l l m a tr ix
l e a s t - s q u a r e s p ro c e d u re was a tte m p te d i n th e sp ace g ro u p , Pn.
F iv e c y c le s o f ORFLSD l e a s t - s q u a r e s re f in e m e n t w ere c a l c u l a t e d ,
b u t co m p le te co n v erg en c e ( a l l p a ra m e te rs s h i f t / e r r o r < 1 . 0 )
c o u ld n o t be a c h ie v e d .
The r e s i d u a l v a l u e s a t t h i s p o i n t w ere
R = 0 .0 6 0 and R = 0 .0 4 4 . By u se o f th e H am ilto n R - f a c to r r a t i o
w
28
te s t,
we can r e j e c t th e h y p o th e s i s t h a t th e c e n tro sy m m e tric
s p a c e g ro u p i s t h e m ore c o r r e c t o f t h e tw o s o l u t i o n s a t th e 99.5%
c o n f id e n c e l e v e l .
The r e s u l t s t e l l u s f t h a t i f we r e j e c t th e
c e n tr o s y m m e tr ic s t r u c t u r e , we w i l l s u b j e c t o u r s e lv e s t o a r i s k
o f r e j e c t i n g th e t r u e h y p o th e s i s l e s s t h a n 0.5% o f th e tim e .
T h is t e s t s u g g e s ts t h a t th e n o n -c e n tro s y m m e tric s t r u c t u r e c o u ld
be c o r r e c t .
H ow ever, s c r u t i n y o f t h e c a l c u l a t e d bond le n g th s
showed t h a t th e v a lu e s f o r t h e Pn m odel d id n o t make s e n s e .
C-N
bond l e n g t h s v a r i e d from 0 .9 5 0 t o 1 .4 0 6 £ and t h e C-C l e n g th s
ra n g e d from 1 .1 8 4 t o 1 .7 5 3
from th e f i f t h
F u r th e r m o r e , th e c o r r e l a t i o n m a t r i x
l e a s t s q u a r e s c y c le i n d i c a t e d by th e l a r g e c o r ­
r e l a t i o n c o e f f i c i e n t s ( > 0 .9 5 ) t h a t atom s i n Pn a r e r e l a t e d b y
a tw o - f o ld a x i s .
T h e r e f o r e , on th e b a s i s o f c h e m ic a l a rg u m e n ts
p r i m a r i l y b a se d on th e w id e ra n g e o f bond a n g le s and b y th e h ig h
c o r r e l a t i o n c o e f f i c i e n t s , th e c o r r e c t s p a c e g ro u p was c h o se n t o
be P 2 /n .
I t s h o u ld a l s o be m e n tio n e d t h a t t h e r e i s a p s e u d o ­
c e n t e r o f sym m etry a t h, h r e l a t i n g th e m o le c u le s i n
p a irs
w h ic h , i f g e n u in e , would
F ig u r e 1
p ro v id e t h e s p a c e g ro u p A 2 /a .
i s a s t e r e o p l o t o f t h e c o m p le ted s t r u c t u r e .
38
S in c e th e c r y s t a l l o g r a p h i c a l l y in d e p e n d e n t u n i t c o n ta i n s
two h a lv e s o f tw o s e p a r a t e m o le c u le s , t h e s t r u c t u r a l d a t e i n th e
f o llo w in g t a b l e s c o n t a i n
and th e w e ig h te d a v e r a g e
v a lu e s fro m m o le c u le o n e , m o le c u le tw o ,
o f t h e tw o. T a b le I l i s t s t h e a t o n i c
c o o r d i n a t e s w i t h t h e i r r e s p e c t i v e th e r m a l p a r a m e te r s .
i n ORFLSD f o r th e o r i e n t a t i o n a n g le s o f r i g i d phenyl
D ata u sed
g ro u p s a r e
FIGURE 1.
The M o le c u la r C o n f ig u r a tio n o f
[Pd (FUMN)(PPh3) 2 ]
TABLE I .
A tom ic C o o r d in a te s and T herm al P a ra m e te r s F o r
[Pd(FUMN)(PPh3) 2 ]
TABLE I .
Atom C o o rd in a te s F o r The [Pd(FUMN) ( P P h ^ j l U sing P2 / n Space Group.
Atom
M olecule #1
Pd 1A
x CIO4 o)
z ( 104 a)
y ( 104 a)
B (10 a
0.2500
*
-0 .2 0 6 1 ( 2 )
0.3 1 9 0 (1 )
*
0 .2 8 9 1 (4 ) '
-0 .5 5 8 5 ( 8 )
0.2 7 3 0 (4 )
4 .0 ( 2 )
C 2
0 .3 1 4 0 (5 )
-0 .5 9 9 3 (10)
0.3457 ( 6 )
5 .4 (2)
N 1
0 .3 2 7 4 (5 )
-0 .6 3 4 7 (10)
0 .4 0 2 4 (5 )
7 .6 (2 )
Phenyl r i n g A**
0.5061 ( 2 )
-0 .3 7 5 6 (4 )
0 .3 5 0 8 (2 )
1 .6 ( 1)
C 3
0.4413
-0 .3 0 4 5
0.3 4 0 4
2 .3 (2 )
C 4
0.4473
-0 .3 5 9 0
0.2819
2 .9 (2 )
C 5
0.5121
-0 .4 3 0 2
0.2 9 2 4
3 .5 (2)
C 6
0 .5 7 0 9
-0 .4 4 6 8
0.3 6 1 2
4 .7 ( 2 )
C 7
0.5 6 4 9
-0 .3 9 2 2
0.4197
6 .0 (3)
C 8
0.5 0 0 1
-0 .3 2 1 1
0.4 0 9 3
4 .6 (2 )
H 4***
0.4051
-0 .3 4 7 1
0.2 3 2 5
6 .0
H 5
0 .5 1 6 4
-0 .4 6 9 4
0 .2 5 0 4
6 .0
0.2 5 0 0
-0 .3 4 4 5 (1 )
P 1
0 .3 5 5 6 (1)
C 1
-
vo
TABLE I .
(Continued)
Atom
x ( 104 a)
7 C10^
z (104 ct)
B (10 ct)
P henyl r i n g A**
H 6
0 .6 1 7 4
-0 .4 9 7 8
0.3687
6 .0
H 7
0.6071
-0 .4 0 4 1
0.4691
6 .0
H 8
0.4958
-0 .2 8 1 9
0.4512
6 .0
0 .3 5 6 6 (2 )
-0 .1 1 9 3
0.4 6 6 6 (2 )
1 .9 (1 )
C 9
0.3599
-0 .1 5 3 3
0.4040
2 .0 ( 2)
C 10
0.3629
- 0 .0 1 0 2
0.4 2 4 6
2 .9 (2 )
C 11
0 .3 5 9 5
0 .0 2 3 8
0.4872
3 .9 (2 )
C 12
0.3532
-0 .0 8 5 3
0.5291
4 .8 (3 )
C 13
0.3 5 0 2
-0 .2 2 8 5
0.5085
6 .3 (3 )
C 14
0.3536
-0 .2 6 2 5
0.4459
5 .0 (2 )
H 10***
0 .3 6 7 4
0 .0 6 8 1
0.3 9 4 5
6 .0
H 11
0 .3 6 1 6
0.1265
0 .5 0 2 0
6 .0
H 12
0 .3 5 0 8
-0 .0 6 0 9
0.5740
6 .0
H 13
0.3457
-0 .3 0 6 8
0.5387
6 .0
Phenyl r i n g B**
ro
o
TABLE I .
(C ontinued)
Atom
x <104 a)
y ( 104 cr)
z ( 104 <j)
B (10 a
P henyl r i n g B**
H 14
P h en y l r i n g C**
0 .3 5 1 5
0 .3 8 6 9 (2 )
-0 .3 6 5 2
0.0 8 1 7 (4 )
0.4 3 1 2
6 .0
0 .2 5 3 6 (2 )
1 . 0 ( 1)
C 15
0 .3 7 4 2
-0 .0 4 2 6
0.2831
2 .5 (2 )
C 16
0 .4 3 8 2
0.0391
0 .3 2 2 5
4 .3 (2 )
C 17
0 .4 5 0 9
0.1 6 3 5
0.2931
4 .4 ( 2 )
C 18
0 .3 9 9 6
0 .2061
0 .2 2 4 2
4 .4 (2 )
C 19
0.3357
0 .1 2 4 4
0 .1 8 4 8
4 .7 ( 2 )
C 20
0 .3 2 3 0
0 .0 0 0 0
0.2 1 4 2
3 .8 (2 )
H 16***
0 .4 7 4 9
0 .0 0 8 5
0.3719
6 .0
H 17
0 .4 9 6 8
0 .2 2 2 1
0 .3 2 1 4
6 .0
H 18
0.4087
0 .2 9 5 4
0.2031
6 .0
H 19
0 .2 9 8 9
0 .1 5 5 0
0 .1 3 4 5
6 .0
H 20
0.2771
-0 .0 5 8 6
0.1859
6 .0
TABLE I .
(Continued)
Atom
M olecule #2
Pd 2A
x (IQ4 O')
y (104 o)
z (104 ct)
B (10 <j)
0.7 5 0 0
-0 .2 1 8 3 (1 )
0 .2 5 0 0
*
P 3
0 .6 5 3 6 (1 )
-0 .3 5 2 5 (2 )
0.1621 ( 1 )
*
C 41
0.7 1 4 2 (5 )
-0 .0 0 5 0 (9 )
0.2169 (4 )
4 .2 ( 2 )
C 42
0.7 1 6 6 (5 )
0 .0 3 2 0 (9 )
0 .1 5 2 4 (5 )
4 .8 ( 2 )
N 3
0.7 1 8 7 (5 )
0 .0 6 2 8 ( 8 )
0.1009 (4)
6 .7 ( 2 )
0 .5 9 7 5 (2 )
-0 .6 4 3 9 (4 )
0.2039 ( 2 )
0 .7 ( 1 )
Phenyl r i n g D**
C 43
0.6207
-0 .5 1 7 1
0.1 8 5 3
3 .0 ( 2 )
C 44
0 .5 5 4 9
-0 .5 8 3 7
0 .1 3 6 4
4 .5 ( 2 )
C 45
0.5 3 1 7
-0 .7 1 0 5
0 .1 5 5 0
4 .7 ( 2 )
C 46
0 .5 7 4 2
-0 .7 7 0 7
0.2 2 2 5
4 .5 ( 2 )
C 47
0 .6 4 0 0
-0 .7 0 4 0
0 .2 7 1 4
4 .3 ( 2 )
C 48
0 .6 6 3 3
-0 .5 7 7 2
0.2 5 2 8
3 .4 ( 2 )
H 44
0 .5 2 4 4
-0 .5 4 0 5
0.0880
6 .0
H 45
0 .4 8 4 4
-0 .7 5 8 3
0 .1 2 0 0
6 .0
H 46
0 .5 5 7 6
-0 .8 6 1 7
0.2359
6 .0
ro
jo
TABLE I .
(Continued)
Atom
x ( 104 ct)
y ( 104
z (104 ct)
B (10 a)
P h en y l r i n g D**
H 47
0 .6 7 0 6
-0 .7 4 7 2
0.3 1 9 8
6 .0
H 48
0 .7 1 0 5
-0 .5 2 9 4
0 .2 8 7 8
6 .0
0.5 0 0 2 (2)
-0 .1 7 1 0
0.0 9 6 3 (2 )
1 .3 ( 1 )
C 49
0 .5 6 6 5
-0 .2 4 8 8
0.1 2 2 4
2 .7 ( 2 )
C 50
0 .5 4 0 8
-0 .1 9 9 6
0.1 6 9 2
3 .4 ( 2 )
C 51
0 .4 7 4 5
-0 .1 2 1 8
0 .1431
4 .7 ( 2 )
C 52
0 .4 3 3 8
-0 .0 9 3 2
0.0701
5 .4 ( 2 )
C 53
0 .4 5 9 5
-0 .1 4 2 4
0 .0 2 3 3
5 .3 ( 2 )
C 54
0 .5 2 5 8
- 0 .2 2 0 2
0 .0 4 9 4
3 .7 ( 2 )
H 50
0.5 7 0 0
- 0 .2 2 0 0
0 .2 2 1 6
6 .0
H 51
0.4 5 6 1
-0 .0 8 6 5
0 .1767
6 .0
H 52
0 .3 8 6 2
-0 .0 3 7 4
0 .0 5 1 3
6 .0
H 53
0 .4 3 0 3
-0 .1 2 1 9
0.0 2 9 1
6 .0
H 54
0 .5 4 4 2
-0 .2 5 5 5
0.0 1 5 9
6 .0
Phenyl r i n g E**
S3
W
TABLE I .
(Continued)
Atom
x ( 104 a)
y ( 104 ct)
z ( 104 ct)
0 .6 8 9 5 (2 )
-0 .4 3 5 4 (5 )
0.0 3 3 3 (2 )
2 .5 (1 )
C 55
0 .6 7 2 4
-0 .4 0 2 8
0.0883
1 .5 (2)
C 56
0.6 9 7 9
-0 .2 9 5 3
0.0592
3 .4 (2)
C 57
0.7 1 5 1
-0 .3 2 7 9
0.0043
4 .4 (3 )
C 58
0.7067
-0 .4 6 8 1
-0 .0 2 1 6
4 .6 (3)
C 59
0.6 8 1 2
-0 .5 7 5 6
0.0074
5 .8 (3)
C 60
0.6 6 4 0
-0 .5 4 3 0
0.0623
4 .0 (2 )
H 56
0.7 0 3 9
-0 .1 9 4 7
0.0778
6 .0
H 57
0 .7 3 3 4
-0 .2 5 0 8
-0 .0 1 6 5
6 .0
H 58
0.7191
-0 .4 9 1 5
-0 .0 6 1 0
6 .0
H 59
0.6 7 5 2
-0 .6 7 6 2
- 0 .0 1 1 2
6 .0
H 60
0.6457
-0 .6 2 0 1
0.0831
6 .0
Phenyl r i n g F**
* A n is tro p ic th e rm a l p a ra m e te rs f o r th e p a lla d iu m and phosphorus
form
B (10 a)
e x p ( - ( h 2 pn
+ k 2 p22 +
+ 2 (hkP 12 + h iP 13 + W P23» ) .
atoms a r e o f th e
TABLE I .
(F o o tn o te s C o n tin u ed )
Atom
105 Bn
1 ° 5 b2 2
1 0 s b3 3
Fd 1A
272 (4)
781 (15)
264 (4 )
0
125 (3 )
P 1
263 (9 )
780 (33)
256 ( 8 )
-2 6 (13)
H I (8 )
Pd 2A
238 (4 )
796 (1 4 )
268 (4 )
0
102 (3 )
P 3
256 (9 )
908 (34)
234 ( 8 )
-7 1 (14)
110 (7 )
1 05 P12
105 s 13
1 0 5 *23
0
-o (1 3 )
0
-5 7 (13)
**The o r ig i n s o f th e p h en y l r i n g s w ere p la c e d a t th e c e n te r o f th e r i n g s i n th e p la n e
o f th e r i n g s .
The te m p e ra tu re f a c t o r s (B) r e p o r te d a r e f o r t h e r i n g and th e in d i v i d ­
u a l l y r e f i n e d a to m ic f a c t o r s .
th e sum o f th e gro u p
The a c t u a l B f o r e ac h atom o f th e g r o u p , t h e r e f o r e , i s
B p lu s th e i n d iv i d u a l r e f i n e d v a lu e .
***The p o s i t i o n s o f th e h y d ro g en s w ere c a l c u l a te d u s in g 1 .0 0 8 a s th e c arb o n -h y d ro g en
bond d i s t a n c e .
lis te d
i n T a b le I I .
i n T a b le I I I .
O bserv ed and c a l c u l a t e d s t r u c t u r e f a c t o r s a r e
Bond l e n g th s and a n g le s a r e p r e s e n te d I n T a b le IV .
The g e o m e t r ic a l d e s c r i p t i o n o f l e a a t s q u a r e s m o le c u la r p la n e s and
t h e i r d i h e d r a l a n g le s l a sum m arized i n T a b le V.
TABLE I I .
E u l e r i a n R o ta tio n A n g le s F o r The R ig id G roups
In
[Pd(FU M N )(PPh^)2 ]
TABLE I I .
E u le r ia n R o ta tio n A ngles ( i n d e g re e s ) F or The Phenyl R ings T re a te d
As R ig id G roups F o r [Pd(FUMN) ( P F h p ^ 3*
Group
0 (10 o)
0 (10 o)
R (10 a)
M olecule #1
P h en y l A
6 4 .6 (3 )
142.1 (2 )
- 9 6 .5 (3 )
Phenyl B
- 6 0 .4 (3 )
1 2 5 .9 (2)
1 5 1 .9 (4 )
Phenyl C
-1 8 7 .0 (3 )
- 1 3 0 .4 (2 )
1 2 5 .4 (3 )
M olecule #2
Phenyl D
- 1 4 .8 (3 )
1 3 8 .2 (2 )
- 1 1 8 .5 (3)
P henyl E
-1 2 9 .8 (3 )
-1 2 9 .8 (2 )
P henyl F
3 1 .4 (3 )
-1 4 1 .2 (2)
7 8 .5
(3)
- 2 9 .9 (3 )
TABLE I I I .
The O bserved And C a lc u la te d S t r u c t u r e F a c t o r s
For
[Fd(FUMN)(PFh3 ) 2 ]
30
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TABLE IV
Bond L e n g th s and A n g le s Found F o r
CFd(FUMN)(PPh3 ) 2 ]
TABLE IV.
Bond L en g th s (A ngstrom s) and Bond A ngles (D eg rees) f o r
[Pd(EUMN)(PPh3) 2 ] .
D ata f o r th e tv o m o le c u le s and t h e i r a v e ra g e v a lu e s a re ta b u la te d .
Bond
M olecule #1
M o lecu le
#2
A verage
Pd - P
2.335
(2)
2.331
(2)
2.333
(1)
Pd - c i b
2.113
(8)
2.116
(8)
2.114
(6)
c i - c r c
1.420
(10)
1.471
(9)
1.448
(7)
C1 - C2
1.428
(14)
1.429
(15)
1.428
(10)
C2 - N
1.147
(16)
1.147
(16)
1.147
(11)
P - C 3d
1.824
(5)
P - C9
1.825
(6)
P - C 15
1.817
(5)
P - C 43
1.826
(5)
1.826
(2)
P - C 49
1.836
(5)
P - C 55
1.843
(6)
TABLE IV.
(Continued)
g
Angle
M olecule #1
M olecule #2
A verage
p - Pd - p
113.0
( 1)
115.2
( 1)
1 14.1
( 1)
Cl - Pd - Cl
3 9 .3
(3 )
4 0 .7
(3 )
4 0 .0
(2)
P - Pd - Cl
103.9
( 2)
1 0 2 .0
(2)
103.0
( 1)
Pd - Cl - C2
1 1 3 .8
(7)
1 1 2 .5
(7)
1 13.2
(5 )
Cl - C2 - N
1 7 3 .8
( 11)
1 7 9 .4
( 12)
1 7 6 .4
( 8)
C l '- Cl - C2
117.2
(9 )
116.8
(9 )
117-0
( 6)
g
A verage v a lu e s w ere c a lc u la te d a s w e ig h te d a v e ra g e s from th e fo llo w in g ,
—
2
B = w^Bj + v 2 B2
w here w = 1 / a
ct = ( 1/ ct^ + 1/
^Numbers on th e c arb o n s c o rre sp o n d t o m o lecu le # 1 ; c o rre sp o n d in g numbers f o r
m o le c u le #2 a r e o b ta in e d by ad d in g 40 t o th e number.
cP rim es ( ' ) in d i c a t e th e two fo ld e d p o s i t i o n o f th e numbered ato m s.
^O nly an o v e r a l l a v e ra g e was c a l c u l a t e d .
TABLE V.
L e a s t- S q u a re s P la n e s D eterm in ed F o r
[Pd(FUMN)(PPh3) 2 ]
TABLE V
L e a s t S quares P la n e s ; The Angle Between T h e ir Normals and The P e rp e n d ic u la r
D is ta n c e o f S e le c te d Atoms Prom The P la n e .
(a )
P la n e
A
M olecule #1
( I ) P d lA -P l-P l*
( Ax + By + Cz = D )
P lan e D e f in iti o n
B
C
D
13 .4 3 6
0 .0 0 0
-2 0 .5 6 1
- 1 .7 8 1
1 2 .2 8 4
0 .0 0 0
-2 0 .8 7 1
-2 .1 4 7
(2)
P d lA -C l-C l 1
(3)
PdlA -Cl-C2
-1 8 .6 8 6
-2 .8 9 9
4 .7 8 5
-2 .4 7 7
(4)
P d lA -P l-C l
13.218
0.197
-2 0 .6 2 4
-1 .9 2 0
(5)
C1-C2-N1
5 .133
-8 .7 5 8
-6 .6 7 7
4 .5 5 2
( 6)
C1-C2-C1'
3 .6 7 4
-8 .8 7 7
-6 .2 4 3
4 ,3 1 6
16.919
0 .0 0 0
-1 8 .5 6 4
8 .0 4 8
17.069
0 .0 0 0
-1 8 .4 2 4
8.196
-1 5 .8 1 1
-3 .0 0 9
-2 .3 0 8
-1 1 .7 7 8
16.984
-0 .0 3 8
-1 8 .5 3 7
8 .0 8 5
-1 7 .4 4 9
2 .9 4 0
1.045
-1 2 .2 5 1
4 .6 0 5
-8 .9 5 8
-4 .9 7 1
2 .2 5 6
M olecule #2
(7) Pd2A -P3-P3'
( 8)
Pd2A-C41-C41'
(9)
Pd2A-C41-C42
( 10)
Pd2A-P3-C41
( 11)
C41-C42-N3
( 12)
C41-C42-C411
TABLE V.
(C ontinued)
(b )
D e v ia tio n s o f Atoms From
P la n e s .
Atom
(1 )
(£ )
(2)
Cl
0 .052
C2
-1 .1 0 8
-1 .2 1 1
N1
-2 .0 9 3
-2 .2 3 0
(7 )
( 8)
C41
0 .0 1 0
C42
1 .2 4 6
1 .228
N3
2 .3 3 9
2 .2 1 3
TABLE V.
(C ontinued)
(c )
D ih e d ra l A n g les.
A ngles Between P la n e s In D egrees
(°).
P la n e s
M olecule #1
A ngles
P la n e s
M olecule #2
A ngles
A rith m e tic
A verage
( 1, 2)
4 .2
( 7 ,8 )
0.8
2 .5
d ;3 )
115.9
( 7 ,9 )
110.8
1 1 3 .4
( 1 , 6)
7 2 .6
(7 ,1 2 )
7 4 .3
7 3 .5
(2 ,3 )
111.9
( 8 ,9 )
1 1 1 .5
111.7
(2, 6)
7 2 .6
( 8 , 12)
7 4 .3
7 3 .5
(3 ,4 )
1 1 5 .6
(9 ,1 0 )
110.8
113.2
(4 ,6 )
7 3 .8
7 4 .1
7 3 .9
( 10 , 12 )
o
DISCUSSION
The u n i t c e l l c o n ta i n s f o u r d i s c r e t e m o le c u le s o f
Pd(PUMN)(PPh )
3 ^
I n d i v i d u a l bond l e n g t h s and a n g l e s I n t h i s com-
pound d o n o t d i f f e r s i g n i f i c a n t l y fro m th e m a j o r i t y o f th o s e
r e p o r t e d i n s i m i l a r com pounds.
B ecau se t h e r e i s no m e a n in g fu l
d i f f e r e n c e i n th e v a l u e s o f th e two h a l f m o le c u le s , th e a v e r a g e
o f t h e s e v a lu e s w i l l be r e p o r t e d .
Two bonds may be c o n s id e r e d
t o d i f f e r s i g n i f i c a n t l y i f A bond > 3 ( ct^
2
+
2 k
) t w here
and a,, a r e th e s ta n d a r d d e v i a t i o n o f bond #1 and bond #2 ( o r
a n g le #1 and a n g le # 2 ) .
T h ere i s one e x c e p tio n t o t h i s c r i t e r i o n
i n T a b le IV w ith th e P - P d - P 1 a n g l e .
No r e a s o n h a s b e e n fo u n d t o
s u g g e s t t h a t t h i s d e v i a t i o n i s an e l e c t r o n i c phenom enon.
The
s u s p e c te d r e a s o n f o r t h i s d i f f e r e n c e i s d ue t o th e s t r a i n im posed
on m o le c u le s packed i n th e s o l i d s t a t e .
C e n t r a l M e ta l C o o r d in a tio n :
Two p h o s p h o ru s
ato m s and tw o o l e f i n c a rb o n ato m s fo rm a
n e a r l y p l a n a r a rra n g e m e n t a b o u t th e c e n t r a l m e t a l.
The a v e r a g e
P d -P bond l e n g t h o f 2 .3 3 3 (1 ) £ i s w i t h i n t h e ra n g e o f v a l u e s
r e p o r t e d i n th e l i t e r a t u r e :
Pd (C l) (C^H^) (P P h^) o f 2 .3 1 ( - ) 5if ^
P d (C l)(C 4 H7 )(P P h 3) o f 2 .3 1 (1 )
30 (TT-C3H5)P d (P P h 3 )S n C l3- 0 . 4 0 M e^O
o f 2 .3 1 7 (3 ) 8 , 31 and Pd(CS2 ) ( P P h ^ o f 2 .4 1 5 ( 8 ) S . 32
The
f u m a r o n l t r i l e lig a n d I s s i t u a t e d i n th e P -P d -P p la n e w ith th e
n o d a l p la n e o f th e . e th y le n e tt sy ste m p e r p e n d ic u la r t o th e m o le c u la r
p la n e .
The Pd-C d i s t a n c e s from th e FUMN a r e 2 .1 1 3 ( 8 ) and 2 .1 1 6
( 8 ) £ and a r e c o n s i s t e n t w ith m e ta l- c a r b o n bond l e n g th s r e p o r te d
f o r a n a lo g o u s m o le c u le s :
2 .12
P d (C l) (C^H^M PPh^) o f 2 .1 0 ( - ) ,
( - ) , and 2 .1 7 ( - ) X , 29 and ( T T - C ^ P d ( P P h p S n C l^ 0 .4 0
Me2 C0 o f 2 .1 1 6 (2 1 ) 8 . 31
The C l- P d - C l' p la n e i s t i l t e d w ith
r e s p e c t t o th e P l - P d - P l ‘ p la n e by a n a v e ra g e a n g le o f 2 .5 ° .
T h is s l i g h t d e v i a t i o n from c o - p l a n a r i t y can p r o b a b ly be a t t r i b u t e d
t o p a c k in g f o r c e s r a t h e r th a n a n y s i g n i f i c a n t e l e c t r o n i c d i s t o r t i o n
i n t h e f u m a r o n i t r i l e t o c e n t r a l m e ta l b o n d s.
E q u iv a le n t d i h e d r a l
a n g le s i n r e l a t e d o l e f i n i c and a c e t y l e n i c compounds a r e found t o
v a r y from 0 .2 t o 8 .3 d e g r e e s .
T r ip h e n y lp h o s p h in e :
The s i x P-C d i s t a n c e s ra n g e from 1 .817 (5 ) t o 1 .8 3 6 (5 )
8 (a v e ra g e i s 1 .8 2 6 (2 ) 8 ) and a g re e w ith P-C bonds r e p o r t e d f o r
r e l a t e d c o m p o u n d s .^
The a v e ra g e P-C bond le n g t h d o es n o t
d i f f e r s i g n i f i c a n t l y from th e v a lu e o f 1 .8 2 8 (5 ) 8 r e p o r te d f o r
th e u n c o o rd in a te d tr ip h e n y lp h o s p h in e m o le c u le .
33
To m in im ize
i n t e r a t o m i c i n t e r a c t i o n s , th e p h e n y l g ro u p s i n th e t r i p h e n y l ­
p h o s p h in e lig a n d s a r e s i t u a t e d i n a p r o p e l l e r a rra n g e m e n t aro u n d
th e phosphorus
a to m s.
The a v e ra g e v a lu e o f th e P d -P -C a n g le i s
1 1 4 .6 (1 1 ) ° and th e a v e ra g e C-P-C a n g le b etw een a d ja c e n t p h e n y l
g ro u p s i s 1 0 3 .8 ( 1 0 ) ° .
No i n d i v i d u a l C-C bond l e n g th s w ere
d e te rm in e d s in c e th e p h e n y l r i n g s w ere t r e a t e d a s r i g i d g ro u p s
and a v a lu e o f 1 .3 9 4 8 was ch o sen a s t h e i n v a r i a n t C-C d i s t a n c e
f o r th e c o u rs e o f r e f in e m e n t.
2 1 -2 3
F u m a ro n ltrile :
The v a lu e s 1 .4 2 8 (1 0 ) and 1 .1 4 7 (1 1 ) 8 w ere found f o r
th e C-CN and C-N a to m ic d i s t a n c e s r e s p e c t i v e l y .
T hese v a l u e s ,
w i t h i n e x p e r im e n ta l e r r o r , a r e n e a r th o s e o f 1 .4 1 6 (1 6 ) and 1 .1 4 5
(1 5 ) X r e p o r t e d f o r Ir (H ) (CO) (FUMN) ( P P h ^ ) ^ * *
The m ost u n iq u e
f e a t u r e i n th e m o le c u le i s th e C-C d i s t a n c e i n th e o l e f i n i c
g ro u p .
The a v e ra g e d i s t a n c e i s found t o be 1 .4 4 8 (7 ) 8 w hich i s
i n te r m e d ia te b e tw ee n 1 .5 4 8 o f th e C-C s i n g l e bond and 1 .3 3 8 o f
th e C-C d o u b le b o n d .
21 -2 3
A c o n s id e r a b le am ount o f b a c k - d o n a tio n
*
from th e m e ta l o r f c i t a l s i n t o th e tt o r b i t a l o f th e f u m a r o n l t r i l e
w ould a c c o u n t f o r th e le n g th e n in g o f th e C-C bond t o su ch an
e x te n t.
35
Pd-FUMN b o n d in g :
U sin g th e P e a rs o n h a r d - s o f t / a c i d - b a s e t h e o r y (HSAB),
th e p a lla d iu m atom c o n ta in s a d * ° e l e c t r o n i c sy ste m and i s co n s id e r e d a v e r y s o f t a c i d .
34
I n th e same m an n er, th e t r i p h e n y l ­
p h o sp h in e and f u m a r o n l t r i l e lig a n d s a r e b o th v e r y s o f t b a s e s .
The PFh^ m o ie ty h a s a lo n e p a i r o f e l e c t r o n s a v a i l a b l e f o r
d o n a tio n t o th e m e ta l o r b i t a l s .
The f u m a r o n l t r i l e h a s a
tt
bonded
s y ste m w h ic h c a n a c t a s a w eak e l e c t r o n d o n o r ; b u t m ore i m p o r t a n t l y f
'ft
i t c o n t a i n s an em pty tt - a n t i b o n d i n g o r b i t a l a t s u f f i c i e n t l y low
e n e r g y to a c t a s a s t r o n g e l e c t r o n a c c e p t o r .
From t h e HSAB c o n c e p t
we know a m ix in g o f a s o f t a c i d w i t h s o f t b a s e s w i l l p ro d u c e a
s t a b l e m o le c u le w hose e l e c t r o n s a r e r e d i s t r i b u t e d so a s t o g a in
t h e maximum s t a b i l i z a t i o n e n e r g y .
T h is d e s c r i p t i o n o f b o n d in g
p r e d i c t s t h a t th e m o le c u le w i l l b e s t a b l e , b u t d o e s n o t d e s c r i b e
t h e m ethod o f b o n d in g .
C usachs and c o -w o rk e rs h a v e p r e s e n te d a m ore c o n c is e
•jf
bon din g scheme f o r TT -bonded m e ta l o l e f i n s com plexes in term s o f
a m o le c u la r o r b i t a l a p p ro a c h .
35
A s c h e m a tic r e p r e s e n t a t i o n o f
th e b o n d in g schem e i s i l l u s t r a t e d
i n F ig u r e 2 .
C o n s id e r in g t r i g o n a l
and s q u a re p l a n a r h y b r id m e ta l o r b i t a l s , C u sach s c o n c lu d e d t h a t
t h e m e ta l dp
2
h y b r id o r b i t a l w as m o st f a v o r a b l e f o r t h i s ty p e o f
com plex b o n d in g .
F ig u r e 2 shows one o f th e t h r e e h y b r id dp
2
o rb i­
t a l s o f t h e m e ta l i n a n o r i e n t a t i o n s u c h t h a t i t c a n p a r t i a l l y
o v e r la p t h e TT c lo u d o f th e FUMN g ro u p .
The o r i e n t a t i o n o f th e
m e ta l d 2 2 o r b i t a l i s c o r r e c t f o r e f f e c t i v e o v e r la p w i t h t h e
x -y
*
TT - a n t i b o n d i n g o r b i t a l o f th e o l e f i n g ro u p .
The n e t e f f e c t o f
t h e s e o v e r la p s i n th e p r e s e n t c a s e i s t o i n c r e a s e th e s y n e r g ic
b o n d in g in t h e Pd-FUMN s y s te m .
e l e c t r o n s t o t h e em pty dp
2
As t h e FUMN tt bond d o n a te s
o r b i t a l o f P d , t h e f i l l e d Pd d^2
2
*
o r b i t a l b a c k - d o n a te s e l e c t r o n s i n t o th e TT o r b i t a l o f FUMN.
R. J o n e s h a s c o n c lu d e d fro m X - r a y a n a l y s i s and i r
s tu d ie s th a t
FIGURE 2 .
C u s a c h 's M odel Of B onding F o r O le f in i c
C om plexes o f T r a n s i t i o n M e ta ls
46
I n co m p lex es o f t h i s s o r t th e tt
a c c e p t i n g a b i l i t y o f th e o l e f i n
i s m ore i n f l u e n t i a l i n s t a b i l i z i n g t h e m e t a l - o l e f i n bond th a n i t s
tt d o n a tin g a b i l i t y .
36
A
T h u s, I f th e FUMN tt o r b i t a l a c c e p ts
e l e c t r o n s and th e tP o r b i t a l d o n a te s c h a rg e d e n s i t y t o t h e dp^
o r b i t a l , a d e c r e a s e i n bond o r d e r w i l l o c c u r i n t h e C-C bond o f
t h e FUMN.
T h is i s t h e tr e n d o b s e rv e d i n t h e p r e s e n t s t r u c t u r e .
The d e g r e e t o w h ich th e bond o r d e r d e c r e a s e s w i l l depend p a r t l y
*
on th e d e g r ee o f o v e r la p o f th e dx 2 - y 2 and tt o r b i t a l s and th e
a v a i l a b i l i t y o f e l e c t r o n s o n th e c e n t r a l m e ta l.
The m e ta l i n
t h i s s tu d y ( P d ( 0 ) ) i s a d ^ ° s y ste m and t h e m e ta l o r b i t a l s c o n t a i n
s u f f i c i e n t e l e c t r o n s w i t h w h ic h t o b a c k - d o n a te .
The o t h e r co n ­
s i d e r a t i o n , th e d e g re e o f i n t e r a c t i o n , d e p en d s on t h e s i z e and
d i r e c t i o n a l p r o p e r t i e s o f th e a to m ic o r b i t a l s and a l s o on th e
e n e r g y d i f f e r e n c e s o f t h e o v e r la p p in g o r b i t a l s .
J o n e s add
*
o th e r s have d em on strated t h a t th e e n e r g y o f th e it o r b i t a l
d e c r e a s e s a s s t r o n g e r a n d / o r l a r g e r num bers o f e l e c t r o n w ith d ra w in g
5 36
g ro u p s a r e p la c e d on t h e o l e f i n c a rb o n s ( F ig u r e 3 ) . *
The two
cy an o g ro u p s on t h e FUMN a r e s t r o n g l y e l e c t r o n w ith d ra w in g and
w ou ld a p p e a r Co f u l f i l l t h e e n e r g y r e q u ir e m e n t an d f a l l i n t h e
r e g i o n i n d i c a t e d i n F ig u r e 3.
C om p ariso n s and C o r r e l a t i o n s :
H aving e s t a b l i s h e d r e a s o n a b l e j u s t i f i c a t i o n f o r a p p ly in g
C u sa c h ’ s m odel o f b o n d in g t o t h e p r e s e n t s t r u c t u r e , c o m p a riso n s
FIGURE 3 .
E n e r g ie s F o r The H ig h e s t O ccu p ied n M o le c u la r
O r b i t a l and Low est Empty U A n tib o n d in g O r b i t a l
Of S e v e r a l O l e f i n s
0 -
TT
1 0 -
20-
30-
TT
53,2
r* 4 o -
TT
o 50-
TT
60.5
io 60-
46.0
o
— 70H
40.5
80H
Lii
90
TT1
TT
TT
io o i
H3Cn
/CH3 H\
/ c ~ C\
H^C
.H
0
yc = C \
CH^ H
H
CN
H,
H
CN
=
H
>
H
TT
H
=
NC
<
CN
c = c
CN
NC
CN
50
and c o r r e l a t i o n s o f th e b o n d in g I n Pd(FUMN) (PPh 3) 2 w i t ^ o th e r
m o le c u le s can f o llo w .
X -ra y s t u d i e s o f t h e a n a lo g o u s
P t (FUMN) (PPh^) j m o l e c u l e ^ a s w e ll a s a n I r id iu m compound,
Ir (H ) (CO) (FUMN) (PPh3) 2^
have b e e n p e rfo rm e d .
A c o m p ariso n o f
p e r t i n e n t bond l e n g th s and a n g le s i s p r e s e n te d I n T a b le V I.
It
sh o u ld be re -e m p h a s iz e d t h a t th e s i n g l e v a lu e s f o r Pd(FUMN)(PPh^)^
a r e w e ig h te d a v e ra g e v a lu e s f o r th e two h a l f m o le c u le s w h ich a r e
r e p o r te d I n t h i s s tu d y .
When th e d a ta o f th e s e t h r e e compounds ( i . e . ,
Pd(FUMN)(PPh3) 2 , Pt(FUMN)(PPh3) 2 , and Ir(H ) (CO)(FUMN)(PPh3 ) 2 w ere
i n i t i a l l y com pared, (T a b le V I) a n a p p a r e n t s h o r te n in g o f th e
m e ta l-p h o s p h o ru s
bond i n t h e p la tin u m compound was o b se rv e d
a lo n g w ith two s i g n i f i c a n t l y d i f f e r e n t C-C bond le n g t h s f o r th e
c h e m ic a lly e q u iv a l e n t m e ta l- c a r b o n bon d s i n th e FUMN.
I t was
s u s p e c te d t h a t t h e X -ra y s tu d y o f th e p la tin u m com plex was
q u e s tio n a b le .
The m e ta l-p h o s p h o ru s
bond i n e a c h o f th e
d e te r m in a tio n s w as found t o be 2 .2 9 ( P t - P ) , 2 .3 3 ( P d - F ) , and
2 .3 2 ft ( I r - P ) .
A s e a r c h th ro u g h th e l i t e r a t u r e p ro v id e d
t h e a v e ra g e v a lu e s o f 2 .2 9 ( P t - P ) , 2 .3 2 ( P d -P ), and 2 .3 5 ft
( I r - P ) and th e v a lu e s found in th e t h r e e s t r u c t u r e s a g re e w e ll
w ith th e s e bond l e n g th s .
I f one lo o k s a t th e p e r i o d i c t r e n d s
o f e f f e c t i v e a to m ic o r i o n i c r a d i i , t h e r e i s a g e n e r a l d e c r e a s e
i n th e s i z e from th e 5d s e r i e s t o th e 6 d s e r i e s o f th e t r a n s i t i o n
e le m e n ts .
T h is w ould a c c o u n t f o r th e d i f f e r e n c e b etw een th e P d -P
TABLE VI
A Summary o f T h re e C om plexes C o n ta in in g The
FUMN L ig an d
TABLE V I.
A Summary o f T hree Complexes C o n ta in in g The FUMN L igand.
D ata Method
[Pd(FUMN)(PPh3) 2 ]
[Pt(FUMN)(PPh3) 2 ]
5.0% P 2 /n
8 .3 % P 2 l / c
D if f r a c to m e te r Mo Ka
F ilm Cu - KOf
[lr(H)(CO)(FUM N)(PFh3 ) 2 ]
5.6% C 2 /c
D if f r a c to m e te r Mo Ka
Bonds
M- P
2 .3 3 3 (1)
2 .2 7 7 ( 5 ) ,2 .2 9 6 ( 4 )
2 .3 1 7 (3 )
M- C
2 .1 1 4 ( 6 )
2 .0 5 ( 2 ) ,2 .1 6 ( 2 )
2 .1 1 0 (9 )
C-C'
1 .4 4 8 (7 )
1 .5 3 (4 )
1 .4 3
(2)
A ngles
P - M- P
1 1 4 .1 (1 )
C - M- C
4 0 .0 (2)
1 0 4 .4 (2 )
114.1
(1 )
4 2 .6 (1 0 )
3 9.7
(5)
5.2^
0.2
P la n e s
P - M- P
vs
2.5
C - M- C
\J]
TO
and P t- P v a l u e s .
H ow ever, one w ould e x p e c t th e s i z e o£ th e
i r i d i u m and p la tin u m t o b e a p p r o x im a te ly t h e sam e.
Even th o u g h
t h i s i s n o t a r a s h a s s u m p tio n , i t m u st be a p p li e d w i t h c a u t i o n
f o r two r e a s o n s .
I n th e c o m p le x e s, th e I r
1+
is a d
8
s y s te m and
th e PtCQ) i s a d ^ °system and th e ato m ic ' s i z e s ' o f t h e s e I n d iv id u a l
s p e c i e s w i l l be s l i g h t l y d i f f e r e n t .
r e a s o n , I s th e s t e r i c e f f e c t .
The seco n d and m ore im p o r ta n t
I n t h e p la tin u m and p a lla d iu m
co m p le x e s, th e s q u a r e p l a n a r a rra n g e m e n t can accom m odate two
c i s - tr ip h e n y lp h o s p h in e l i g a n d s w ith o u t h i n d r a n c e .
The sym m etry
o f th e l i g a n d s a b o u t th e i r i d i u m i s o c t a h e d r a l and i n t h i s
c o n f i g u r a t i o n , th e m e t a l - l i g a n d bond l e n g t h s a r e s e n s i t i v e t o
s te ric e ffe c ts .
T h is s e n s i t i v i t y t o s p a t i a l a rra n g e m e n t o f
li g a n d s a b o u t a c e n t r a l m e ta l i s i l l u s t r a t e d
In th e c a se o f
I r ( H ) (CO) (FUMN) ( P P h ^ g ^ w h ere t h e m e ta l-p h o s p h o ru s
d is ta n c e
i s 2 .3 1 7 (3 ) 2 and i n th e more s t e r i c a l l y h in d ered
Ir(B r)(C O )(T C N E )(P P h 3 ) 2
12
(w h ere TCNE = t e t r a c y a n o e t h y l e n e )
th e a v e r a g e m e ta l-p h o s p h o ru s
bond i s 2 .4 0 0 (3 ) S .
T h u s, th e
r e s u l t s o f th e s e t h r e e s t u d i e s a r e c o n s i s t e n t w i t h th e l i t e r a t u r e
v a l u e s f o r m e ta l-p h o s p h o ro u s d i s t a n c e s , and t h e i r r e l a t i v e
m a g n itu d e s can be r a t i o n a l i z e d by b o th p e r i o d i c t r e n d s and
s te r ic e ffe c ts .
C o r r e l a t i o n s o f t h e m e ta l- c a r b o n d i s t a n c e s i n t h e s e
compounds a r e g e n e r a l l y f u t i l e , and no c o m p a riso n o f t h e s e
v a l u e s , s i m i l a r t o t h e c o m p a riso n f o r m e ta l-p h o s p h o ru s
bonds,
c a n be made s in c e t h e e r r o r s f o r t h e m e t a l- c a r b o n d i s t a n c e s a r e
la rg e .
The r e s o l u t i o n f o r l i g h t ato m s i n th e im m e d ia te v i c i n i t y
o f h e a v y m e ta ls i s p o o r and n o m e a n in g fu l c o n c lu s io n s c a n be
draw n u n t i l m ore p r e c i s e d i f f r a c t i o n d a t a a r e o b ta i n e d .
N e v e rth e ­
l e s s , th e d i f f e r e n c e b e tw ee n t h e m e ta l- c a r b o n bond l e n g t h s
r e p o r t e d f o r t h e P t com plex ( 2 .0 5 (2 ) and 2 .1 6 (2 ) 8 ) i s a p p a r e n t l y
s ig n ific a n t.
T hese two b o n d s s h o u ld b e c h e m ic a lly e q u i v a l e n t
and no s i g n i f i c a n t d i f f e r e n c e i s e x p e c te d t o e x i s t b e tw e e n th em ;
t h e r e f o r e , i t i s p o s s i b l e t h a t t h e a p p a r e n t d i f f e r e n c e i s due
t o an e r r o r i n t h e Pt(FU M N )(PPh^)^ s t r u c t u r e .
F our p o s s ib le so u rc e s o f e r r o r have been i d e n t i f i e d ,
and i n d i v i d u a l l y o r i n t o t o may c o n t r i b u t e t o th e p r o d u c ti o n
o f th e s p u r io u s r e s u l t s r e p o r t e d by P a n a t t o n i e t a l .
T h e ir d a t a
w e re d e r iv e d fro m m ic r o d e n s i to m e t r i c m e asu re m e n ts o f e m u ls io n
f il m s and a r e , t h e r e f o r e , i n h e r e n t l y l e s s a c c u r a t e t h a n d i f ­
fra c to m e te r d a ta .
A n o th e r s o u r c e o f e r r o r w ould r e s u l t fro m t h e
f a c t t h a t a c y l i n d r i c a l a b s o r p t i o n c o r r e c t i o n was a p p l i e d t o t h e
d a t a a n d , a lth o u g h t h i s may n o t b e a b ad e s t i m a t i o n o f th e
c r y s t a l s h a p e , i t i s s t i l l a n a p p ro x im a tio n to t h e a c t u a l s h a p e .
The e r r o r d u e t o t h i s c o r r e c t i o n i s n o t a n t i c i p a t e d t o c o n t r i b u t e
e x t e n s i v e l y t o th e r e s u l t i n g d i f f e r e n c e b u t , n e v e r t h e l e s s , i s a n
a d d i t i o n a l s o u rc e o f e r r o r i n t h s s t r u c t u r e d e t e r m i n a t i o n .
A
t h i r d s o u r c e i s t h e o m is s io n o f th e im a g in a ry p a r t o f th e
anom olous d i s p e r s i o n c o r r e c t i o n made f o r t h e p la tin u m ato m .
T h is
c o r r e l a t i o n m o d if ie s th e c a l c u l a t e d p h a se o f th e s t r u c t u r e f a c t o r
and th u s d i r e c t l y a f f e c t s th e a to m ic p o s i t i o n s .
No j u s t i f i c a t i o n
f o r t h i s o m is s io n was made by th e a u t h o r s and t h i s
so u rc e o f e r r o r .
i s a g e n u in e
The l a s t and p e r h a p s m ost s i g n i f i c a n t o f th e s e
f o u r p o s s i b l e s o u r c e s o f e r r o r may be due t o i n c o r r e c t s e l e c t i o n
o f th e s p a c e g ro u p .
The sp ac e g ro u p o f th e P t co m p lex was
r e p o r t e d t o b e P 2 ^ /c
i s P 2 /n .
5
, n o . 14)
39
b u t i n th e Pd a n a lo g u e i t
I t w as p o in te d o u t e a r l i e r t h a t a c e n t e r o f sym m etry
a lm o s t e x i s t s i n th e Pd com plex u n i t c e l l a t (Ag,
% ), and i f
g e n u in e , th e n o n c e n tro s y m m e tric s p a c e g ro u p , P n , c o n s id e r e d i n
t h e s o l u t i o n o f th e Pd com plex w ould become P 2 ^ /c upon a s im p le
tra n s fo rm a tio n o f a x e s.
T h is p se u d o i n v e r s i o n c e n t e r r e l a t e s
v e r y c l o s e l y t h e Pd and P atom s i n th e tw o h a l f - m o l e c u l e s o f th e
a sy m m e tric u n i t , b u t th e l i g h t e r atom s a r e n o t a s c l o s e l y r e l a t e d .
I f th e i n v e r s i o n c e n t e r , r e p o r t e d i n th e P t co m p lex , w ere a c t u a l l y
a p s e u d o i n v e r s i o n c e n t e r , th e n t h e p la tin u m and p h o sp h o ru s
a to m s w ould be c l o s e l y r e l a t e d b y t h e i n v e r s i o n o p e r a t i o n w h ile
t h e FUMN g ro u p w ould n o t b e .
The s o l u t i o n o f t h e s t r u c t u r e u s in g
t h e i n c o r r e c t s p a c e g ro u p c o u ld r e s u l t i n d i s t o r t i o n s o f th e bond
l e n g t h s and a n g le s i n t h e FUMN g ro u p .
F u r t h e r e v id e n c e s u p p o r tin g th e f a c t t h a t t h e r e s u l t s
o f t h e P t com plex may n o t be l e g i t i m a t e comes fro m th e f o llo w in g
o b s e rv a tio n .
I t was p o in te d o u t e a r l i e r t h a t , a s t h e num ber o f
e l e c t r o n e g a t i v e g ro u p s on th e e th y le n e i s i n c r e a s e d , th e c l o s e r
56
th e e n e rg y l e v e l s o f th e o l e f i n tt
each o th e r.
and m e ta l d o r b i t a l s a p p ro a c h
I f t h i s i s th e c a s e , th e o v e r la p o f t h e s e two s e t s
o f o r b i t a l s sh o u ld i n c r e a s e , c a u s in g th e C-C e th y le n e bond t o
le n g th e n .
I n T a b le V II t h i s in c r e a s e i s o b s e rv e d i n th e
Ir(H )(CO )(FU M N )(PPh 3 ) 2 and Ir(B r)(C O )(T C U E )(P P h 3 >2 co m p lex es,
w here th e C-C l e n g th s a r e 1 .4 3 1 (2 0 ) and 1 .5 0 6 (1 5 ) 8 r e s p e c t i v e l y .
H ow ever, lo o k in g a t th e c o rre s p o n d in g P t com plexes o f Pt(FUMN)(PPh 3 ) 2
and Pt(TC N E)(PPh3) 2 » whose r e p o r te d e th y le n e bond le n g th s a r e
1 .5 3 (4 ) and 1 .4 9 (5 ) 8 r e s p e c t i v e l y , t h i s t r e n d i s n o t p r e s e r v e d .
T h e r e f o r e , i t i s c o n clu d e d t h a t th e r e s u l t s f o r th e FUMN C-C
and P t-C bond d i s t a n c e s in th e Pt(FUMN)(PPh 3 ) 2 com plex a p p e a r t o
be i n c o r r e c t .
57
TABLE V II.
A Summary Of C y a n o - S u b s titu te d O le f in Com plexes
Of
P d , P t , and I r
TABLE V II.
A Summary o f C y a n o -S u b s titu te d O le f in Complexes o f Pd, P t, and I r
Bonds i n 8
M olecule
M- P
M- C
Pd(FUMN)
2 .3 3 5 (2 )
2 .33 1 (2)
2 .1 1 3 ( 8 )
2 .1 1 6 ( 8 )
Pt(FUMN)
2.277 (5 )
2 .2 9 6 (4)
2 .0 5
2 .1 6
Pt(TCNE)
2 .2 9 1 (9 )
2 .2 8 8 ( 8 )
2.12
2.10
Ir(FUMN)
Ir(TCNE)
A ngles in ( ° )
P - M- P
C - M- C
1 .4 2 (1 )
1.4 7 (1 )
1 1 3 .0 (1)
1 1 5 .2 (1 )
3 9 .3 (3 )
4 0 .7 (3 )
(2)
(2)
1 .5 3 (4 )
1 0 4 .4 ( 2 )
4 2 .6 ( 1 0 )
10
(3)
(3)
1 .4 9 (5 )
1 0 1 .4 (3)
4 1 .5 (13)
15
2.317 (3 )
2 . 1 1 0 (9 )
1 .4 3 (2 )
114.1 (1 )
3 9 .7 (5 )
11
2 .4 0
2 .1 5
1 .5 1 (2 )
1 1 0 .4 ( - )
1 0 3 .6 ( - )
4 1 .0 ( - )
12
(-)
(-)
C -C
R eferen c e
P r e s e n t Work
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G. H. S to u t and L. H. J e n s e n , "X-Ray S t r u c t u r e D e t e r m in a t io n ,"
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G.
B. C a r p e n te r , " P r i n c i p l e s o f C r y s t a l
S t r u c t u r e D e te r m in a t io n ,"
W. A. B e n ja m in , I n c . , New Y o rk , 1969.
1 9.
EXECXRAY *67 C om puter S c ie n c e P ro g ram c o m p iled b y
th e
U n i v e r s i t y o f M a ry la n d , 1967.
2 0.
S. F . W a tk in s, "RBANG, A CDC F o r t r a n 63 Com puter P ro g ram F o r
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I ) , U n i v e r s i t y o f W isc o n s in , 1967.
2 1.
L . P a u l i n g , "The C h em ical B o n d ," C o r n e l l U n i v e r s i t y P r e s s ,
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H. J . M. Bowen, " T a b le s o f I n t e r a t o m i c D is ta n c e s and Con­
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C. W e a st, "H andbook o f C h e m is try and
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H. G o l d s t e i n , " C l a s s i c a l M e c h a n ic s ," A d d iso n -W esle y P r e s s ,
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W. R. B u sin g , K. 0 . M a r tin and H. A. L ev y , "ORFLS, A
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(b )
ORFLSD i s an e x t e n s i v e m o d i f i c a t i o n o f ORFLS.
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CHAPTER I I .
THE X-RAY STRUCTURE DETERMINATION
OP
TRICYANOMETHANIDO-N-CARBONYLBIS(TRIPEHNYLPHOSPHINE) IRIDIUM ( I )
[ir(T C M )(C O )(P Ph3) 2 ]
62
INTRODUCTION
As e a r l y a s 1886, th e tric y a n o m e th a n i.d e a n io n (TCM) was
p re p a re d and s t u d i e d ; ^ b u t i t was n o t u n t i l 1962 t h a t a c o n v e n ie n t
p r e p a r a t i o n f o r t h i s a n io n was e s t a b l i s h e d
2
and a n i n t e r e s t in
t h i s t r i v a l e n t c a rb o n c o n ta in in g m o le c u le e n su e d . The sodium
3
A £
“J
(NaTCM), p o ta s s iu m (KTCM),
and ammonium (NH^TCM) s a l t s w ere
s tu d ie d b y v a r io u s m etho d s and among th e s e was X -ray c r y s t a l l o g ­
ra p h y .
I t was found t h a t a l l t h r e e c r y s t a l s t r u c t u r e s w ere
p o ly m e ric and w ith th e e x c e p tio n o f th e NH^+ compound, a l l w ere
ju d g e d t o d i s p l a y a t r i g o n a l p l a n a r a rra n g e m e n t f o r th e t r i cyan o m eth an id e io n .
F o llo w in g th e s tu d y o f th e a l k a l i m e ta l s a l t s , th e n e x t
m o le c u le s t o be s tu d ie d w ere th e t r a n s i t i o n m e ta l compounds.
Compounds o f M n (I), M n (II) , F e ( I I ) , F e ( I I I ) , C o ( I I ) , N i ( I I ) ,
8 _
C u ( I I ) , and A g (I) w ere p re p a re d and t h e i r p r o p e r t i e s s t u d i e d .
I n a l l th e compounds, a t r i g o n a l p la n a r c o n f i g u r a t i o n f o r th e TCM
io n was p r e d ic te d by s tu d y in g th e i n f r a r e d sp e c tru m i n th e
-1
2150 - 2250 cm
r e g io n .
Two o f th e s e com pounds, th e AgCCCCN)^)
and t h e CuCcCCN)^^ m o le c u le s , w ere i n v e s t i g a t e d f u r t h e r by
X -ra y d i f f r a c t i o n .
9 13
*
+
T h e r e s u lts o f t h e s e s t u d i e s show ed, a s
+
+
i n th e c a s e o f th e Na , K , and NH^
63
s a l t s , a p o ly m e ric s t r u c t u r e
f o r th e m e ta l compounds.
I n th e s o l i d s t a t e , I t a p p e a re d t h a t th e
m ost s t a b l e c o n f i g u r a t i o n was th e p o ly m e ric p a c k in g o f th e s e
m o le c u le s .
O nly a few monomers w ere p re p a re d and th o s e o n ly in
s o lu tio n .
B ad d ley and L en ard a to o k a u n iq u e a p p ro a c h in u t i l i z i n g
t h e TCM
io n
a s a lig a n d in t r a n s i t i o n m e ta l co m p lex es.
14
They p re p a re d and i s o l a t e d some c r y s t a l l i n e , m onom eric com plexes
o f ir i d iu m , rh o d iu m , p a lla d iu m , and p la tin u m c o n ta in in g th e t r i c y an o m e th a n id e io n .
The s tu d y o f th e b o n d in g b etw een th e m e ta l
and th e TCM lig a n d was p erfo rm ed w i t h t h e a id o f i n f r a r e d and
nmr s p e c t r a l d a t a .
The c o n c lu s io n th e y re a c h e d was t h a t th e
TCM group was p l a n a r and bonded to e a c h m e ta l b y a k e te n im in a to
lin k a g e , i . e . , th ro u g h th e n i t r o g e n atom i n th e TCM g ro u p .
How-
e v e r , some d i f f i c u l t y was e n c o u n te re d e x p la in in g th e h ig h
(2005 cm *) c a rb o n y l s t r e t c h i n g fr e q u e n c y i n t h e Ir(TCM) (CO) ( P P h ^ j
compound.
Two d i s t i n c t s t r u c t u r e s c o u ld e x p l a i n t h i s u n u s u a l
s tr e tc h in g freq u e n cy .
I f th e TCM g ro u p w ere s i t u a t e d t r a n s t o
t h e c a r b o n y l, th e n th e i n c r e a s e i n th e s t r e t c h i n g fr e q u e n c y o f
th e CO w ould be a c c o u n te d f o r i f th e d ic y a n o k e te n im in a to lig a n d
w ere a v e r y s tr o n g p i - a c c e p t o r .
The a l t e r n a t i v e s t r u c t u r e o f f e r e d
was t h a t o f a c i s c o n f i g u r a t i o n c i t i n g th e e m p ir ic a l c r i t e r i o n
o f Kemmit and B la n d ,
15
v i z . , t h a t i n th e i n f r a r e d r e g io n o f th e
sp e c tru m from 1570 - 1590 cm * two b a n d s due t o t h e
lig a n d
are p r e s e n t , and i f th e h ig h er en erg y band i s th e more in t e n s e ,
c i s s te r o c h e m is tr y i s p r e s e n t.
A d d itio n a l e v id e n c e fo r the c i s
c o n fig u r a t io n came from the nmr s p e c t r a l data o f Ir(TCM) (CO)(FMePhg^
w hich was made from th e Ir(TCM) (CO) (P P h ^ g compound.
The X -ra y s tu d y o f t h i s compound, Ir(TCM) (CO) (P P h^)^ was
u n d e rta k e n i n o r d e r t o c l a r i f y w h e th e r t h e m o le c u le e x h i b i t s th e
c i s o r t r a n s c o n f i g u r a t i o n and t o a tte m p t t o d e s c r ib e th e mode o f
b o n d in g o f th e TCM and c a r b o n y l g ro u p s t o t h e i r i d iu m atom .
CRYSTAL DATA
The i r r e g u l a r l y shaped c r y s t a l o f [ir(TC M ) ( CO) ( PPh_) „
J 2
C,
O
(w here TCM i s tric y a n o m e th a n id e io n and PPhg *,fl tr i p h e n y lp h o s p h in e )
u sed i n d a ta c o l l e c t i o n was p a le y e llo w and a p p ro x im a te ly 0 .3 0 x
0 .2 0 x 0 .3 0 mm. i n s i z e .
The compound c r y s t a l l i z e s i n th e t r i c l i n i c
sy ste m w i t h C c e n te r e d c e l l c o n s ta n ts o f a a 2 2 ,6 7 7 ( 1 9 ) ,
b = 11.5 5 0 ( 1 2 ) , c = 1 7 .0 1 0 (1 5 ) 8 , a = 8 0 .2 1 ( 1 0 ) , 0 = 9 5 .9 4 ( 7 ) ,
Y = 9 2 .1 4 ( 6 ) ° (w here th e number i n p a r e n th e s e s d e n o te s th e e r r o r
i n th e
l a s t s ig n ific a n t
u n i t s . S in c e
th is
fig u re ), V
= 4366 8 , 3 and Z = 4 fo rm u la
c e l l was found t o
b e Cc e n t e r e d ,
th e
p r im a tiv e
re d u c ed c e l l was c a l c u l a t e d and th e l a t t i c e c o n s ta n t s f o r t h i s
c e l l w ere found to be a = 1 1 .6 1 5 ( 9 ) , b = 1 2 .5 6 2 ( 9 ) , c = 1 6 .9 7 6
(1 2 ) 8 , a = 9 1 .2 4 ( 7 ) , 0 = 9 9 .4 6 ( 5 ) , y = 1 1 4 .9 1 ( 6 ) ° , V = 2204 8 , 3
and Z = 2 fo rm u la u n i t s w ith Fqqq = 866 e l e c t r o n s .
The t r a n s ­
fo rm a tio n m a tr ix em ployed i n th e t r a n s i t i o n from th e C c e n te r e d
c e l l t o t h e p r i m i t i v e re d u c e d c e l l was a l e f t handed m u l t i p l i e r
o f th e form .
h
M
b
*
w here
, and
M|
p
«/
0
brv'
%
-
1
k
0
o
0
0
1
**
a r e t h e p r i m i t i v e re d u c e d c e l l a x e s and
fa,
and £, a r e th e C c e n te r e d a x e s .
B ecause o f th e s o lv a te d
c o n d itio n o f th e compound, a d e n s i t y d e te r m in a tio n b y th e f l o t a t i o n
te c h n iq u e was I n c o n c lu s iv e .
The c a l c u l a t e d d e n s i t y assu m in g two
-3
fo rm u la u n i t s p e r u n i t c e l l was d e te rm in e d to be 1 .3 2 g .c m .
A s p h e r i c a l a b s o r p tio n c o r r e c t i o n was a p p lie d t o th e
re d u c e d i n t e n s i t i e s s in c e th e c a lc u la te d l i n e a r a b s o r p t i o n co ­
e ffic ie n t
f o r X = 0 .7 1 0 7 8 ) f o r th e compound was 3 3 .5 3 cm"*'
and a ssu m in g a r a d i u s (R) o f 0 .1 2 5 mm., r e s u l t e d i n a v a lu e o f
0 .4 2
f o r uR
^max
*T h is v a lu e o f
uR
^max
was s u f f i c i e n t l y la r g e t o
J
w a r r e n t th e a b s o r p t i o n c o r r e c t i o n .
The o n ly s y s te m a tic a b s e n c e s d is p la y e d on th e e m u lsio n
f il m s w ere h k £ , h + k = 2n + I .
T hese a b se n c e s c o rre sp o n d e d t o
a C c e n te r e d c e l l and a t t h i s p o in t th e re d u c e d p r i m i t i v e u n i t
c e l l was c a l c u l a t e d i n o r d e r t o s i m p l i f y th e m apping p ro c e d u re
i n th e s o l u t i o n o f th e s t r u c t u r e and l a t e r r e f in e m e n t.
The p r e ­
lim in a r y s o l u t i o n wsb p e rfo rm ed i n th e sp a c e g ro u p , P I ( c j ,
num ber 2
fits
^ ).
However, s p a c e group
P I ( c j , number 1
a ls o
th e r e f l e c t i o n d a ta and was e v e n t u a l l y t e s t e d a g a i n s t th e
c e n tro s y m m e tric s p a c e g ro u p , P I , and i t was found t h a t th e m ost
l i k e l y o f th e tw o sp ac e g ro u p s i s P I .
EXPERIMENTAL PROCEDURE
The p a l e y e llo w c r y s t a l s w ere r e c r y s t a l l i z e d in a
m ix ed s o lv e n t sy ste m c o n s i s t i n g o f b e n ze n e and h e x a n e .
T h is was
do n e by d i s s o l v i n g a s m a ll am ount o f sam p le i n b e n ze n e and a d d in g
h e x a n e u n t i l th e s o l u t i o n j u s t tu rn e d c lo u d y .
The r e s u l t i n g
c r y s t a l s , w h ich form ed i n t e n days upon p a r t i a l e v a p o r a tio n o f
t h e s o lv e n t , w ere w e ll sh ap ed and t r a n s p a r e n t .
H ow ever, o v e r a
p e r io d o f a w eek, th e m a t e r i a l became opaque and t e x t u r e d l i k e
lump s u g a r .
I n i t i a l l y , w hen a c r y s t a l w as exam ined u s in g
W e isse n b e rg f i l m te c h n iq u e s , i t d is p la y e d a good d i f f r a c t i o n
p a tte rn .
The same c r y s t a l , a f t e r t u r n i n g op aq u e, w as no lo n g e r
a s i n g l e c r y s t a l and no d i f f r a c t i o n p a t t e r n was o b s e r v e d .
At
t h i s tim e i t was s u s p e c te d t h a t e i t h e r th e g a s e s o f th e a i r w ere
r e a c t i n g w ith th e c r y s t a l o r t h a t a s o l v e n t m o le c u le was e s c a p in g
fro m th e c r y s t a l l a t t i c e c a u s in g i t t o c o l l a p s e , th u s r e n d e r in g
th e m a t e r i a l n o n - c r y s t a l l i n e .
I n o rd e r t o p re v e n t t h i s
' d e c r y s t a l l i z a t i o n , ' w h ite g lu e was u sed t o c o a t th e e n t i r e
c ry s ta l.
T h is r e t a r d e d th e g r o s s d e s t r u c t i o n o f th e compound
c r y s t a l l i n i t y f o r th e e n t i r e f i v e w eeks o f d a ta c o l l e c t i o n .
A s e r i e s o f r o t a t i o n , e q u i i n c l i n a t i o n W e isse n b e rg , and
p r e c e s s i o n p h o to g ra p h s w ere ta k e n u s in g Mb K a r a d i a t i o n
(X = 0 .7 1 0 7 £ ) i n o r d e r t o o b ta i n th e c r y s t a l o r i e n t a t i o n and
t o d e f in e a u n i t c e l l .
la ttic e
B ecau se o f t h e c lo s e n e s s o f th e r e c i p r o c a l
l e v e l s , o n ly t h e z e r o l e v e l o f e a c h m a jo r p r e c e s s i o n zone
w as o b ta in e d .
Once t h e o r i e n t a t i o n o f th e c r y s t a l was e s t a b l i s h e d ,
t h e c r y s t a l w as t r a n s f e r e d t o an E n r a f N onius PAD-3 f o u r c i r c l e
d iffra c to m e te r.
T h re e r e f l e c t i o n s w e re c a r e f u l l y c e n te r e d u s in g
t h e m ethod p r e v i o u s l y d e s c r i b e d ( s e e C h a p te r I , E x p e rim e n ta l
P r o c e d u re ) and p ro g ram ORIENT
18
w as u se d to g e n e r a t e o r i e n t a t i o n
a n g le s and a s u b s e t o f a l l th e g e n e r a l r e f l e c t i o n s on t h e a s s u m p tio n
o f a p rim itiv e c e l l .
S e v e r a l a tte m p t s w ere made t o i d e n t i f y
a n d c h a r a c t e r i z e th e r e f l e c t i o n s b u t no r e f l e c t i o n s o u t o f th e
O kl p la n e c o u ld be fo u n d .
At t h i s p o i n t , an a s s u m p tio n was made
t h a t th e 'a * a x i s o f th e c r y s t a l was a c t u a l l y tw ic e a s lo n g .
B ased on t h i s a s s u m p tio n , th e e m u ls io n f i l m s w e re
r e in d e x e d
and
i t was found t h a t t h e r e w e re a b s e n c e s i n th e g e n e r a l h k l d a ta o f
h + k = 2n + 1.
T h is c o rre s p o n d s t o a C c e n te r e d l a t t i c e .
P ro g ram
REDUCELIj^^ d e te r m in e d th e p r i m i t i v e re d u c e d c e l l c o n s t a n t s and
t h e s e v a l u e s w e re u sed i n th e d a ta c o l l e c t i o n and r e f in e m e n t.
T w enty r e f l e c t i o n s w ere c a r e f u l l y o r i e n t e d by th e
t o p / b o t t o m - l e f t / r i g h t c e n t e r i n g t e c h n i q u e (C h a p te r I , E x p e rim e n ta l
P r o c e d u re ) and u se d i n ORIENT t o o b t a i n a l e a s t - s q u a r e s f i t o f t h e
l a t t i c e p a r a m e te r s an d o r i e n t a t i o n a n g l e s f o r t h e c r y s t a l .
l e a s t - s q u a r e s v a l u e s w e re in p u t t o DIFSET
18
T h ese
w h ic h g e n e r a te d c o n t r o l
c a r d s f o r th e a u to m a ted d a ta c o l l e c t i o n .
The two t h e t a (2 6 ) s c a n te c h n iq u e was em ployed
19
w ith
a s c a n ra n g e , A9, d e te rm in e d by
A0 = h (ACON + BCON ( t a n 6 ) ) ,
w here ACON and BCON a r e c o n s ta n t s s e t a t 1 .8 0 and 1 .0 0 r e s p e c t i v e l y
and 6 i s th e t h e t a o r i e n t a t i o n a n g le f o r peak i n t e n s i t y f o r an
in d iv id u a l r e f l e c t i o n .
T h is r e s u l t e d i n a s c a n ra n g e o f a b o u t
one and one h a l f d e g r e e s .
I n th e auto m ated d a ta c o l l e c t i o n , th e f o llo w in g seq u en ce
o f e v e n ts was e x e c u te d f o r e a c h r e f l e c t i o n .
The f o u r o r i e n t a t i o n
a n g l e s , t h e t a , p h i, c h i , and omega, w ere s e t a u t o m a t i c a l l y by
th e m ach in e.
A b a c k la s h c o r r e c t i o n f o r th e g e a r d r i v e s was made
f o r th e t h e t a , p h i , and c h i (omega h e ld a t th e n u l l v a lu e ) by
d e c r e a s in g th e a n g le p o s i t i o n ( i n c r e a s i n g f o r c h i ) by 0 ,5 d e g re e s
and th e n r e t u r n i n g t o th e p eak maximum s e t t i n g .
W ith th e a n g le
s e t t i n g s a t th e p eak maximum, t e n a t t e n u a t o r s , from maximum t o
z e r o a t t e n u a t i o n , w ere p la c e d i n th e p a th o f th e d i f f r a c t e d beam
and f i v e second r a d i a t i o n c o u n ts w ere ta k e n f o r e a c h a t t e n u a t o r .
I f th e number o f c o u n ts ex ceed ed 700 c o u n ts p e r s e c o n d , t h a t
a t t e n u a t o r was s e l e c t e d , th e t h e t a a n g le was d e c r e a s e d by %A
d e g re e s.
A tw e n ty second r a d i a t i o n c o u n t was ta k e n t o e s t a b l i s h
th e s i z e o f t h e back g ro u n d b e f o r e th e sc a n and th e 6 - 2 0 sca n
was begun a t a r a t e o f 0 .5 d e g re e s p e r m in u te .
When th e scan
was co m p le ted , a se c o n d , tw e n ty second b ack g ro u n d c o u n t was
71
c o n d u c te d .
Upon c o m p le tio n o f t h i s c y c l e , th e n e x t r e f l e c t i o n was
s e t i n p o s i t i o n f o r d i f f r a c t i o n and th e c y c le begun anew .
In
t h i s m anner 5179 r e f l e c t i o n s w ere c o l l e c t e d .
T hree s ta n d a rd r e f l e c t i o n s w ere i n s e r t e d i n th e d a ta
c o l l e c t i o n e v e ry 97 c o l l e c t e d r e f l e c t i o n s t o a id i n m o n ito r in g
random o r s y s te m a tic f l u c t u a t i o n s i n th e m easured i n t e n s i t i e s .
I n t h i s way a n y change due t o d e c o m p o s itio n ,
movement o f th e
c r y s t a l , o r any g e n e r a l v a r i a t i o n c o u ld be m o n ito re d .
Program DIFDAT
18
c a l c u l a t e d n e t i n t e n s i t i e s and t h e i r
s ta n d a rd d e v i a t i o n s from th e raw d a ta by
V e t)
- ° I - ( t ( a o a n ) / ( t B1 + t B2 ) ) ( C Bl + CB2 >
and,
ct ( I ) = (Cx + ( t ( s c a n ) / ( t B1 + t B2 ) ) 2 (Cfil + CB2) ) ^
w here Cx , CBX, and Cg2 a r e th e t o t a l c o u n ts , c o u n ts b e f o r e th e
s c a n , and c o u n ts a f t e r th e sc a n and t ( s c a n ) , t BX, and t B2 r e p r e ­
s e n t th e tim e f o r s c a n n in g th e r e f l e c t i o n and tim e f o r back g ro u n d
c o u n ts b e f o r e and a f t e r th e r e f l e c t i o n s c a n .
L o r e n tz and p o l a r ­
i z a t i o n c o r r e c t i o n s w ere a p p lie d t o th e n e t i n t e n s i t i e s in th e
form
L
= (1 + c o s 2 ( 2 0 ) ) / 2 ( s i n ( 2 0 ) ) ,
and s t r u c t u r e f a c t o r s (F ) and t h e i r r e s p e c t i v e e r r o r s ( a ( F ) )
w ere th e n c a l c u l a t e d :
F = ( I ( n e t ) / L P) ) ^
and,
72
cr(F) = c r(i) / (2 .0 (L p * I ( n e t ) ) ^ ) .
The h , k , 1 , F , and a (F ) I n f o r m a tio n was th e n punched on c a r d s f o r
u s e i n th e s o l u t i o n o f th e s t r u c t u r e .
SOLUTION OF THE STRUCTURE
Of th e d a ta c o l l e c t e d , 3928 r e f l e c t i o n s had i n t e n s i t i e s
g r e a t e r th a n 2 a ( I ) , and t h e s e w ere used i n th e c a l c u l a t i o n o f a
P a t t e r s o n i n t e r a t o m i c v e c t o r map.
i r i d i u m atom and one p h o sp h o ru s
19
From t h i s m apping, th e
atom w ere lo c a t e d .
A fo u rie r
d i f f e r e n c e map ( F ( o b s e r v e d ) - F ( c a l c u l a t e d ) ) was c a l c u l a t e d and
th e r e s u l t s p ro d u c e d a r e s i d u a l f a c t o r (R) o f 0 .2 7 .
From t h i s
map, atom s i n th e p h e n y l r i n g s a s w e l l a s th e seco n d p h o sp h o ru s
atom w ere l o c a t e d .
By a s e r i e s o f d i f f e r e n c e m aps, whose p h a s e s
w ere d e r iv e d from p r e v io u s m aps, s e v e r a l o f th e c a rb o n atom s in
t h e p h e n y l r i n g s w ere p o s i t i o n e d .
The p h e n y l r i n g s o f th e tr ip h e n y lp h o s p h in e g ro u p s w ere
th e n t r e a t e d a s r i g i d g ro u p s .
T h is m ethod in v o lv e s d e f i n i n g a
f i x e d model f o r th e group ( i . e . , a p l a n a r , s i x membered r i n g )
w i t h a n o r i g i n and th r e e E u l e r i a n a n g le s d e f i n i n g th e group
o r i e n t a t i o n w ith r e s p e c t t o th e c r y s t a l l o g r a p h i c o r i g i n .
RBAN6
20
Program
was th e n u sed t o d e te rm in e th e o r i e n t a t i o n a n g le s f o r
e a c h g ro u p .
By u s in g th e r i g i d group m ethod, th e number o f
v a r i a b l e p a ra m e te rs was re d u c e d i n th e f i n a l a n a l y s i s from 410
t o 146.
21
Once th e p h e n y l r i n g s w ere d e f in e d , OKFLSD
was used
t o c a r r y o u t th e l e a s t - s q u a r e s a n a l y s i s em p lo y in g th e r i g i d g ro u p
m eth o d .
F o u r c y c le s w ere n eeded t o d ro p th e R f a c t o r t o a v a lu e
o f 0 .1 3 9 ,
In a su bseuqent f o u r ie r d iff e r e n c e s y n th e s is , fo u r
maxima w ere found t h a t c o rre sp o n d e d t o th e c a rb o n y l g ro u p and
one cyano group o f th e TCM l i g a n d .
t h a t th e ir i d iu m and tw o p h o sp h o ru s
th e rm a l m o tio n .
I n t h i s map, i t was o b se rv e d
atom s e x h ib i te d a n i s o t r o p i c
Two c y c le s o f l e a s t - s q u a r e s w ere c a l c u l a t e d
b a se d on th e p o s i t i o n s o f th e i r i d i u m , two p h o s p h o ru s,
s ix
p h e n y l r i n g s , th e c a r b o n y l, and one cyano group o f th e TCM.
A n is o tr o p ic m o tio n c o r r e c t i o n s w ere made f o r th e i r i d iu m and
p h o sp h o ru s
atom s and th e d a ta w ere w e ig h te d by a f a c t o r
w = 1 / ( ct ( F ) ) 2 .
The r e s i d u a l f a c t o r R and w e ig h te d r e s i d u a l f a c t o r
w ere
0 .1 1 3 and 0 .1 2 4 .
By a l t e r n a t e l y c a l c u l a t i n g f o u r i e r d i f f e r e n c e maps and
p e rfo rm in g l e a s t - s q u a r e s , th e l o c a t i o n o f th e re m a in in g atom s and
th e m o le c u la r c o n f i g u r a t i o n w ere c h a r a c t e r i z e d .
However, th e
i s o t r o p i c th e rm a l p a ra m e te rs o f ato m s N3 and C3 w ere 1 6 .9 5 and 1 3 .0 3
re s p e c tiv e ly .
T hese v a lu e s a r e much l a r g e r th a n e x p e c te d and
s u g g e s te d t h a t so m eth in g was s t i l l i n c o r r e c t i n th e r e f in e m e n t
m odel ev en th o u g h R was 0 .0 8 6 and R^ was 0 .0 8 4 .
B ecau se o f th e s u s p e c te d p re s e n c e o f a s o lv e n t m o le c u le ,
a d i f f e r e n c e map was s t u d i e d , s e v e r a l la r g e p eak s w ere lo c a t e d
a b o u t th e p o in t ( ^ , ^ , 0 ) i n th e u n i t c e l l , and a s o lv e n t m o le c u le ,
b e n ze n e , w as i d e n t i f i e d .
T h ree c y c le s o f l e a s t - s q u a r e s , t r e a t i n g
th e b e n ze n e a s a r i g i d g ro u p , p ro d u ced R = 0 .0 7 7 and R^ = 0 .0 6 6 .
The n e x t s t e p in th e r e fin e m e n t o f th e d a ta was t o
a p p ly a n a b s o r p tio n c o r r e c t i o n .
employed f o r s e v e r a l r e a s o n s .
An a p p ro x im a te c o r r e c t i o n was
The l i n e a r a b s o r p tio n c o e f f i c i e n t
(ji) and t h e a v e ra g e r a d i u s f o r th e c r y s t a l (RmflV) p ro d u ced
llR
^ max
= 0 .4 2 , w hich i s a n i n d i c a t i o n t h a t a b s o r p t i o n l u s t b o rd e rs
on s i g n i f i c a n c e .
A n o th er r e a s o n f o r th e a p p ro x im a te c o r r e c t i o n
was th e f a c t t h a t th e c r y s t a l was c o a te d w i t h g lu e , w hich made
in d e x in g o f th e c r y s t a l f a c e s im p o s s ib le .
The shape o f t h e
c r y s t a l w as a p p ro x im a te ly c u b ic , 0.025cm on a n e d g e , b u t an
a d e q u a te e s ti m a te o f t h i s sh ap e was a s p h e re o f r a d iu s 0.0125cm .
S e v e ra l l e a s t - s q u a r e s c y c le s r e s u l t e d i n R = 0 .0 7 9 and
= 0 .0 6 4 ,
i n d i c a t i n g th e a b s o r p tio n to b e o f m in im al im p o rta n c e .
I n d i f f r a c t i o n a n a y l s i s o f t h i s ty p e , th e a ss u m p tio n i s
made t h a t th e e n e rg y o f th e X- r a y p h o to n s i s much g r e a t e r th a n
th e b in d in g e n e rg y o f th e e l e c t r o n s in th e i n d i v i d u a l atomB.
However, i f th e im p in g in g p h o to n s have a w a v e le n g th j u s t l e s s
th a n t h a t o f th e a b s o r p t i o n edge o f an atom , th e n t h i s i s no
lo n g e r a v a l i d a ss u m p tio n .
C hanges o c c u r i n t h e s c a t t e r e d i n ­
t e n s i t i e s i n b o th p h a se and m a g n itu d e .
T h is change i n th e
s c a t t e r i n g power o f a n atom i s c a l l e d anom olous d i s p e r s i o n .
22
To c o r r e c t f o r t h i s , th e s c a t t e r i n g f a c t o r s o f th e a f f e c t e d atom s
m ust be m o d ifie d to
76
f = f° + A f ’ + i A f 1
w here f ° i s th e
’n o rm a l' s c a t t e r i n g f a c t o r v a l u e , A f 1 i s th e
r e a l p a r t o f th e anom olous s c a t t e r i n g , and A £ ’ ’ i s th e Im a g in a ry
p a rt.
Two c y c le s o f r e fin e m e n t w ith a n anom olous d i s p e r s i o n
c o rre c tio n fo r
th e ir i d iu m atom w ere c a r r i e d o u t and th e a g r e e ­
m ent f a c t o r s dropped t o R = 0 .0 6 9 and
= 0 .0 6 2 .
A t t h i s p o i n t , i t was o b s e rv e d t h a t e a c h s e t o f th r e e
s ta n d a r d s s y s t e m a t i c a l l y d e c re a s e d i n i n t e n s i t y d u r in g th e d a ta
c o lle c tio n .
The t h r e e s e t s w ere p l o t t e d on a c h a r t a s lo g o f
i n t e n s i t y v e r s u s tim e and f o r a l l t h r e e r e f l e c t i o n s , as th e tim e
o f c o l l e c t i o n in c r e a s e d , a s te a d y d e c r e a s e in l o g ( I ) was n o te d .
T h is d e c l i n e a p p e a re d t o b eh av e a s a f i r s t o r d e r d e c a y .
On
t h i s a s s u m p tio n a c o r r e c t i o n was a p p li e d to th e i n t e n s i t i e s in
th e form
I ( c o r ) = I o (e k tn )
w here
I ( c o r ) = c o rre c te d in te n s ity
Iq
= m easu red i n t e n s i t y
k
= d e ca y c o n s ta n t
t
= tim e p e r r e f l e c t i o n
n
= number o f th e r e f l e c t i o n .
The v a lu e o f t was e s tim a te d t o be 0 .0 8 3 h o u rs p e r r e f l e c t i o n and
th e v a lu e o f k , 2 .2 6 x 10
-4
hr
-1
, w as found b y ta k i n g an a v e ra g e
o f s e v e r a l k v a lu e s c a l c u l a t e d f o r e a c h o f th e t h r e e r e f l e c t i o n s :
77
k = 2 .3 ( lo g I t - lo g I 2 ) / t .
T h is c o r r e c t i o n w as a p p lie d i n program DIFDAT,
18
and a n o b se rv e d
r e f l e c t i o n was e s t a b l i s h e d a s one whose n e t i n t e n s i t y was g r e a t e r
t h a n t h r e e tim e s i t s s ta n d a r d d e v i a t i o n .
I n t h i s m an n er, 2936 d a ta
p o i n t s w ere e s t a b l i s h e d a s b e in g o b serv ed r e f l e c t i o n s .
A f te r rem oving 357 p ie c e s o f d a t a t h a t w ere n o t w e l l r e ­
c o rd e d , th e c o m p le te model w as l e a s t - s q u a r e s f o r f o u r c y c le s and
r e s u l t e d i n R = 0 .0 5 8 and R^, = 0 .0 6 2 .
A n o th e r d i f f e r e n c e map
was r u n w ith a l l th e atom s p o s i tio n e d e x c e p t th e C3 and N3 ato m s.
The map d is p la y e d f o u r maxima i n th e r e g io n w here th e cyano
g ro u p C3-N3 w as l o c a t e d .
Two new r i g i d g ro u p s w ere d e f in e d ,
e a c h r e p r e s e n t i n g one h a l f o f th e cyano g ro u p CN3.
The o r i g i n
o f th e f i r s t r i g i d cyano g ro u p was p la c e d on th e group c a rb o n
and t h a t o f th e sec o n d was on th e group n i t r o g e n .
a s a p r e c a u tio n a r y m e asu re .
T h is w as done
I f i n th e l e a s t - s q u a r e s r e f in e m e n t
th e tw o cyano g ro u p s t r i e d t o co n v erg e t o t h e same l o c a t i o n , th e
l e a s t - s q u a r e s m a t r i x would become s i n g u l a r .
U sing t h i s m odel and
e l i m i n a t i n g 136 re d u n d a n t p ie c e s o f d a ta le a v i n g 2386 r e f l e c t i o n s ,
f o u r c y c le s o f OKFLSD w ere com puted r e s u l t i n g in c o n v erg en ce t o
f ix e d l o c a t i o n s w ith f i n a l a g re em e n t f a c t o r s R = 0 .0 5 3 , R^ = 0 .0 5 1 ,
and ERF - 4 .3 5 8 w h ere EEF = S w (F
o
- F ) 2/(2 3 8 6 - 1 1 3 ).
c
The s o l u t i o n o f th e s t r u c t u r e up t o t h i s p o in t had b een
c o n s tr a in e d t o t h e c e n tro s y m m e tric sp ace g ro u p , P I .
However,
t h e r e i s a n o th e r s p a c e group w h ich i s a l s o c o n s i s t e n t w ith th e
a b s e n c e s re c o rd e d I n th e f i l m w ork.
sp ac e g ro u p , P I .
T h is i s th e n o n c e n tro sy m m e tric
T h e r e f o r e , a second m o le c u le i n th e u n i t c e l l
was g e n e r a te d by th e in v e r s i o n o p e r a tio n and th e n e a c h a to m ic
and r i g i d group p o s i t i o n was moved s l i g h t l y ( i n a random m anner)
from t h a t l o c a t i o n t o p r e v e n t a s i n g u l a r m a tr ix from fo rm in g i n
th e l e a s t - s q u a r e s p r o c e s s .
The a v e ra g e p o s i t i o n o f th e two h a l f
CN3 g ro u p s was used a s th e in p u t f o r CN3 i n t h i s r e f in e m e n t.
Four
c y c le s w ere ru n and th e r e s i d u a l f a c t o r s became R = 0 .0 5 5 and
Rw = 0 .0 4 7 w ith ERF = 4 .0 5 6 , w here ERF = £ w(F q - Fc ) /( 2 3 8 6 - 1 4 5 ).
The H a m ilto n R - f a c t o r r a t i o t e s t
m odels f i t th e d a ta b e t t e r .
23
was u sed t o t e s t w hich o f th e
The r e s u l t s showed th e n o n c en tro sy m -
m e t r i c c a s e i s p ro b a b ly th e c o r r e c t s t r u c t u r e 99.5% o f th e tim e .
How ever, i n th e n o n c e n tro sy m m e tric m odel co n v erg en c e ( s h i f t / e r r o r
< 1 .0 ) o f th e a to m ic p o s i t i o n s c o u ld n o t be a c h ie v e d .
F u rth e r,
th e bond le n g th s and a n g le s f o r th e two in d e p e n d e n t m o d els made
no c h e m ic a l s e n s e .
B ecause o f p h y s ic a l and n o t s t a t i s t i c a l
r e s u l t s , th e c e n tro s y m m e tric m odel was ch o sen a s th e b e t t e r o f
th e tw o m o d e ls.
At t h i s p o in t i n th e p ro b le m , i t was n o t d e te rm in e d
w h e th e r th e CN3 group o f th e TCM p a r t o f th e m o le c u le was d i s ­
o rd e re d o r d is p l a y i n g a b n o rm a lly l a r g e th e rm a l m o tio n .
In o rd e r
to r e s o l v e t h i s q u e s t i o n , a l e a s t - s q u a r e s c a l c u l a t i o n was p e r ­
form ed w ith a n i s o t r o p i c m o tio n f o r e a c h atom o f th e TCM g ro u p .
F o r th e CN3 cyano g ro u p , an a v e ra g e o f th e 'd i s o r d e r e d ' p o s i t i o n s
was u se d t o d e f in e th e c a rb o n and n itr o g e n p o s i t i o n s .
The r e s i d u a l
f a c t o r s , a f t e r t h r e e c y c le s , d ro p p ed t o R = 0 .0 5 2 and
= 0 .0 5 0
w ith t h e ERF = 4 .3 1 7 , w here ERF = E w(F q - F c ) 2 /(2 3 8 6 - 1 4 3 ).
u s in g th e H a m ilto n t e s t ,
23
w ould e q u a l l y f i t t h e d a t a .
By
i t was co n clu d ed t h a t e i t h e r m odel
F ig u r e 5 shows a n end on th e view
o f th e s e two m odels w ith o n ly t h e ir id iu m , p h o sp h o ru s,
th e c e n t r a l
c a rb o n o f th e TCM, and th e two te r m in a l cy an o g ro u p s o f th e TCM.
T h is d ia g ra m c l e a r l y i l l u s t r a t e s how th e two m odels e a c h a c c o u n t
f o r th e e l e c t r o n d e n s i t y in th e r e g io n o f t h i s u n iq u e cyano
g ro u p .
S in c e e i t h e r m odel a p p e a rs t o a c c o u n t f o r th e d a ta
e q u a l l y w e l l , th e r e s u l t s f o r b o th m odels w i l l be p r e s e n t e d .
The a to m ic p o s i t i o n s f o r b o th th e d is o r d e r e d and i s o t r o p i c
m odels a r e in T a b le V I I I .
E u l e r i a n a n g le s and p o s i t i o n a l p a r a ­
m e te rs f o r th e r i g i d g ro u p s a r e p re s e n te d i n T a b le IX.
The ob­
s e rv e d and c a l c u l a t e d s t r u c t u r e f a c t o r s a r e found i n T a b le X.
Bond l e n g th s and a n g le s a r e t a b u l a t e d i n T a b le XI and l e a s t - s q u a r e s
p la n e s i n T a b le X II.
TABLE V III.
A tom ic C o o rd in a te s and Therm al P a ra m e te rs F o r
[lr(T C M )(C O )(PPh3 ) 2 ] ' k CgHg
TABLE V I I I .
(a ) Atomic C o o rd in a te s F or The D iso rd e re d Model o f [ir(T C M )(C O )(P Ph_)„]»
£ £
Atom
x (10 4 a )
y ( 1 0 4 <j)
z (10 4 a )
bo
B (10 a)
Ir
0 .3 2 7 4
(1 )
0.1 6 1 8
( 1)
0.2501
(1 )
*
PI
0.2179
(5 )
0.2299
(4)
0.3 2 6 5
(3 )
*
P2
0.4186
(5 )
0 .0 9 4 8
(4)
0.1597
(3 )
*
Ml
0 .1 8 2 8 (15)
0.0010 (14)
0 .2 3 0 1
( 8)
5.7 (3 )
N2
0.0042 (16)
-0 .3 2 5 2 (15)
0 .0 6 8 8 ( 11 )
8 .0 (4)
Cl
0 .1 0 1 8 (18)
-0 .0 9 6 1 (18)
0 .2 1 5 8 (10)
4 .7 (4 )
C2
0.0083 (1 6 )
-0 .2 7 2 1 (16)
0.1 2 4 9 (12)
5 .5 (4 )
C4
0 . 0 1 1 0 (16)
-0 .2 1 1 7 (15)
0 .1 9 0 4 (10)
4 .7 (4 )
0.4 4 9 1 (20)
0 .3 0 2 3 (16)
0.2 6 2 2 (13)
5 .2 (4 )
CO
0.4491
0 .3 0 2 3
0.2622
4 .0 ( 6 )
01
0.5326
0.3966
0 .2 7 0 0
4 .0 (4)
C arbonyl
oo
TABLE V III.
(Continued)
x (104 a)
y (104 a)
z (104 a)
-0 .0 9 8 1 (40)
-0 .2 5 1 5 (34)
0.2256 ( 22 )
2 . 2 (7)
C83
-0 .0 9 8 1
-0 .2 5 1 5
0.2256
4 .0 (9 )
N83
-0 .1 8 6 3
-0 .3 0 0 3
0.2558
4 .1 (7 )
-0 .1 1 6 1 (38)
-0 .3 4 4 2 (32)
0.2916 ( 22 )
4 .4 ( 8 )
Atom
Cyano 83
Cyano 93
B (10 ct)
C93
-
0.0560
-0 .2 8 7 7
0.2470
2 . 8 (9 )
N93
-0 .1 1 6 1
-0 .3 4 4 2
0.2916
4 .8 (9 )
Phenyl Ring
A * *
0.1 7 0 3
( 8)
0.4331
( 8)
0.2371
( 6)
3 .4 ( 2 )
C5
0.1 8 7 4
0.3441
0.2778
3 .2 (5)
C6
0.1 9 4 3
0.4429
0.3207
2 .9 (5)
C7
0.1 7 7 2
0.5319
0.2800
5 .1 ( 6 )
C8
0.1 5 3 2
0.5221
0.1 9 6 4
6 . 1 ( 6)
C9
0.1463
0.4232
0.1 5 3 5
3 .0 (5 )
03
(O
TABLE V III.
(Continued)
Atom
x (10
ct)
y (10
ct)
z (104 a)
B (10 ct)
Phenyl Ring A**
CIO
0 .1 6 3 4
0.3 3 4 2
0.1942
3 .3 (5 )
H6 ***
0 .2 1 1 5
0.4 5 0 0
0.3807
6.0
H7
0.1822
0.6 0 2 8
0 .3 1 0 8
6.0
H8
0.1410
0.5 8 5 9
0.1672
6.0
H9
0.1291
0.4161
0.0935
6.0
H10
0 .1 5 8 5
0 .2 6 3 3
0 .1 6 3 4
6 .0
Phenyl Ring B**
0.3636
( 8)
0.3337
(5 )
0.5086
(5 )
2 .5 ( 2 )
C ll
0.3 0 1 6
0.2 8 8 4
0 .4 2 9 8
CO
*
CM
C l2
0.4 3 0 2
0 .3 0 8 4
0.4553
4 .0 (4 )
C13
0.4921
0.3537
0.5342
4 .9 (5 )
C14
0.4256
0.3790
0.5875
3 .7 (4)
C15
0.2971
0.3590
0 . 5619
4 .7 (4 )
(4 )
00
UJ
TABLE V III.
(Continued)
Atom
x (104 ct)
y (104 ct)
z (104 cr)
B (10 ct)
Phenyl R ing B**
C16
0.2 3 5 1
0.3137
0.4 8 3 1
4 .6 (5 )
H1 2 **
0.4779
0 .2 9 0 2
0.4 1 7 1
6.0
HL3-'
0 .5 8 4 3
0.3 6 8 0
0 .5 5 2 5
6.0
H14
0.4 7 0 1
0 .4 1 1 5
0 .6441
6.0
HIS
0 .2 4 9 4
0 .3 7 7 2
0.6002
6.0
HI 6
0 .1 4 2 9
0 .2 9 9 4
0.4647
6.0
P h en y l Ring C**
0 .0 6 1 8
( 8)
0 .0 3 9 8
(7)
0.3489
(4 )
2 .6 (2)
C17
0.0 5 7 5
0 .1 2 5 3
0.3382
2 .5 (4)
Cl 8
0 .0521
0 .0 3 4 0
0.3 8 4 8
3 .6 (4 )
C19
0 .0 6 7 3
-0 .0 5 1 5
0 .3 9 5 6
4 .3 (4 )
C20
0.1812
-0 .0 4 5 7
0 .3 5 9 6
4 .8 (5 )
C21
0.1757
-0 .0 4 5 6
0.3129
5 .4 (5 )
CD
TABLE V III.
(C ontinued)
Atom
Phenyl Ring C**
C22
H18***
x (1 0 4 a)
y (104 a )
z (104 a)
B (10 ct)
- 0 . 0564
0.1311
0.3 0 2 2
3 .7 (4 )
0 . 1338
0.0 2 9 9
0 .4 1 0 6
6.0
HI 9
- 0 . 0712
-
0.1170
0.4290
6.0
H20
- 0 . 2668
-0 .1 0 7 0
0.3 6 7 3
6.0
H21
- 0 . 2574
0.0497
0.2 8 7 2
6.0
H22
- 0 . 0524
0.1 9 6 6
0.2 6 8 7
6.0
0. 2097 (18)
0 .0 1 8 6
C23
0 . 3026
0 .0 5 0 9
0 .0 6 5 3
0 .4 (3 )
C24
0. 2565
-0 .0 6 0 9
0 .0 2 4 8
3 .2 (4 )
C25
0. 1636
-0 .0 9 3 2
-0 .0 4 5 6
4 .2 (4 )
C26
0. 1168
-0 .0 1 3 6
-0 .0 7 5 5
5 .1 (4 )
P henyl R ing D**
(7 )
-0 .0 0 5 1
(5 )
2 .6 ( 2)
CD
Ul
TABLE V III.
(C ontinued)
Atom
P h en y l Ring D**
C27
x (104 o)
y (1 0 4 ci)
z (104 a)
B (10 ct)
0 .1 6 2 8
0 .0 9 8 2
■0.0350
5 .5 (5)
C28
0.2557
0 .1 3 0 4
0 .0 3 5 4
5 .0 (4)
H24***
0.2901
-0 .1 1 8 0
0 .0 4 6 2
6.0
H25
0.1 3 0 6
-0 .1 7 3 4
•0.0747
6.0
H26
0.0 5 0 2
-0 .0 3 6 8
■0.1260
6.0
H27
0.1292
0 .1 5 5 3
■0.0564
6.0
H28
0.2887
0.2107
0.0 6 4 5
6.0
P h en y l R ing E**
0.6888
( 8)
0 .2 8 7 3
(7 )
0 .1 2 1 1
(5 )
2.0 ( 2)
C29
0.5 7 2 6
0.2 0 1 3
0 .1 3 5 9
2 . 8 (4 )
C30
0 .5 8 1 0
0 .2 3 7 5
0 .0 5 9 2
3 .4 (4 )
C31
0.6971
0.3 2 3 5
0 .0 4 4 4
4 .3 (4 )
C32
0.8049
0 .3 7 3 2
0 .1063
5 .4 (5)
CD
Ov
TABLE V III.
(Continued)
Atom
P henyl Ring E**
C33
x (10
A
cr)
y
(10
A
a)
z (104 a)
B (10 a )
0 .7 9 6 5
0.3 3 7 0
0 .1 8 3 0
5 .0 (5 )
C34
0 .6 8 0 4
0.2511
0 .1 9 7 8
3 .4 (4 )
H30***
0 .5 0 3 6
0.2 0 1 8
0 .0 1 4 8
6. 0
H31
0.7 0 3 1
0.3 4 9 4
•0.0107
6. 0
H32
0.8 8 8 2
0.4349
0.0957
6. 0
H33
0.8739
0.3727
0 .2 2 7 4
6.0
H34
0 .6 7 4 4
0.2251
0 .2 5 2 8
6.0
0.4867
-0 .1 1 9 5
0 .2 0 6 5
2 . 6 ( 2)
C35
0.4610
-0 .0 2 3 5
0 .1871
1 .3 (4 )
C36
0.4220
-0 .0 8 0 8
0.2540
2 .8 (4 )
C37
0.4477
-0 .1 7 6 7
0 .2 7 3 5
5 .2 (5 )
C38
0 .5 1 2 4
-0 .2 1 5 5
0.2 2 6 0
5 .3 ( 6 )
Phenyl Ring F**
00
sj
TABLE V III.
(Cont in u e d )
Atom
Phenyl Bing F**
C39
x <104 a)
y (104
ct)
z (10 4 ct)
B (10 ct)
0 .5 5 1 4
-0 .1 5 8 2
0.1590
5 .4 (5 )
C40
0.5257
-0 .0 6 2 2
0.1396
3 .5 (4 )
H36**
0.3756
-0 .0 5 3 0
0.2881
6. 0
H37
0 .4 1 9 8
-0 .2 1 7 8
0 .3 2 1 5
6. 0
H38
0 .5 3 0 8
-0 .2 8 4 4
0.2399
6.0
H39
0 .5 9 7 8
-0 .1 8 6 0
0.1250
6.0
H40
0 .5 5 3 6
-
0.0212
0.0916
6.0
0.5 0 0 0
0 .5 0 0 0
0.0000
4 .7 (4)
C41
0.5546
0.5167
-0 .0 6 8 6
4 .0
C42
0.4 2 0 6
0 .4 5 9 4
-0 .0 7 5 5
4 .0
C43
0.3660
0.4427
-0 .0 0 6 9
4 .0
C44
0 .4 4 5 4
0.4833
0.0686
4 .0
Benzene**
CD
CD
TABLE V III.
(C ontinued)
Atom
B enzene**
C45
x C IO 4 <y)
y C IO 4 cr)
z CIO4 a)
B (10 a)
0 .5 7 9 4
0.5406
0.0755
4 .0
C46
0.6340
0.5 5 7 3
0.0069
4 .0
H41***
0.5 9 3 8
0.5287
-0 .1 1 7 8
6. 0
H42
0.3 6 3 7
0.4302
-0 .1 2 9 7
6.0
H43
0.2699
0.4 0 1 6
-0 .0 1 1 9
6.0
H44
0 .4 0 6 2
0.4713
0 .1178
6.0
H45
0 .6 3 6 3
0 .5 6 9 8
0.1297
6. 0
H46
0.7301
0 .5 9 8 4
0.0119
6. 0
00
vO
TABUS V III.
(C o n tin u e d )
(b) Atomic C o o rd in a te s For th e A n is o tr o p ic Model o f [ir(TCM ) (CO) ( P P h ^ ^ l *
Atom
x ( 104 o)
y ( 104 a)
z ( 104 a )
B (1C
Ir
0 .3 2 7 4
(1 )
0.1 6 1 9
(1)
0.2501
( 1)
*
PI
0 .2 1 7 9
(5)
0 .2 2 9 9
(5)
0 .3 2 6 6
(3)
*
P2
0.4 1 8 7
(5)
0.0 9 5 1
(4 )
0 .1 5 9 6
(3)
*
N1
0 .1 8 1 0 ( 2 0 )
0 .0 0 0 2 (1 7 )
0 .2 3 0 0
( 8)
*
N2
0 .0 0 3 6 (18)
-0 .3 2 4 1 (17)
0 .0 7 0 8 (13)
*
N3
-0 .1 5 9 8 (39)
-0 .3 1 8 8 (2 8 )
0 .2 7 1 6 (19)
*
Cl
0 .0 9 9 4 (2 5 )
-0 .1 0 3 0 (24)
0 .2 1 3 6 (11)
*
C2
0.0 0 9 7 (21)
-0 .2 7 0 0 ( 2 1 )
0.1 2 8 3 (16)
*
C3
-0 .0 8 4 8 (33)
-0 .2 7 1 4 (25)
0 .2 3 6 6 (17)
*
C4
0 .0 0 7 9 (20)
-0 .2 1 4 7 (19)
0.1907 (13)
*
o
TABLE V III.
(Continued)
ct)
z (104 a)
0. 4507 (20)
0 .3 0 3 3 (17)
0.2 6 2 0 (14)
5 .2 (4 )
CO
0. 4507
0 .3 0 3 3
0.2620
4 .1 (7 )
Cl
0 . 5330
0.3 9 8 3
0 .2 6 9 8
4 .0 (4 )
Atom
C arbonyl
P henyl Ring A**
x
(1 0 4
0. 1700
a)
( 8)
y (LO4
0 .4 3 3 1
( 8)
0 .2 3 7 4
( 6)
B (10 a)
3 .6 ( 2 )
C5
0. 1872
0 .3 4 4 4
0 .2 7 8 4
2 .3 (5 )
C6
0. 1945
0.4 4 3 8
0.3210
3 .2 (5)
C7
0 . 1773
0.5325
0 .2 8 0 0
5.7 ( 6 )
C8
0. 1528
0.5219
0 .1 9 6 4
5 .9 ( 6 )
C9
0. 1455
0 .4 2 2 5
0.1537
3 .0 (5 )
CIO
0. 1627
0.3337
0.1947
3 .7 (5)
H6 ***
0. 2121
0 .4 5 1 4
0 .3 8 1 0
6.0
H7
0. 1826
0.6039
0.3106
6.0
vo
TABLE V III.
(C ontinued)
Atom
Phenyl R ing A**
H8
x (1 0 4 cr)
y (I 0 4 ct)
z (104 o)
B (10 o)
0 . 1405
0 .5 8 5 6
0.1670
6.0
H9
0. 1279
0 .4 1 4 8
0 .0937
6.0
H10
0. 1574
0 .2 6 2 4
0 .1641
6.0
P henyl R ing B**
0 . 3639
( 8)
0 .3 3 3 6
(5 )
0 .5 0 8 4
(5 )
2 .4 ( 2 )
C ll
0. 3016
0.2 8 8 0
0 .4 2 9 5
2 .3 (4 )
C12
0 . 4300
0.3 0 7 8
0 .4 5 5 0
3 .6 (4 )
Cl 3
0 . 4922
0 .3 5 3 4
0 .5339
4 .7 (5)
C14
0. 4261
0.3 7 9 2
0 .5 8 7 3
4 .1 (5 )
CIS
0. 2978
0 .3 5 9 4
0 .5 6 1 8
5 .3 (5 )
C16
0. 2355
0 .3 1 3 8
0 .4 8 3 0
4 .7 (5 )
H12**
0. 4774
0 .2 8 9 3
0.4167
6.0
HI 3
0. 5843
0.3 6 7 6
0 .5 5 2 1
6.0
M
TABLE V III.
(C o n tin u ed )
Atom
P henyl Ring B**
H14
x (10 4 <j)
y (10 4 a)
z (10 4 ct)
B (10 a)
0.4 7 0 8
0.4 1 1 9
0 .6439
6. 0
H I5
0.2503
0.3779
0.6 0 0 2
6. 0
H I6
0 .1 4 3 4
0.2 9 9 6
0.4647
6. 0
P henyl Ring C**
-0 .0 6 1 8
( 8)
0.0 3 9 9
(7 )
0 .3 4 8 8
(4 )
2 .5 (2 )
C17
0 .0 5 7 5
0 .1 2 5 5
0.3381
2 .3 (4)
C18
0 .0 5 2 0
0.0 3 4 2
0 .3 8 4 8
3 .3 (4 )
C19
-0 .0 6 7 2
-0 .0 5 1 3
0.3955
4 .0 (4 )
C20
-0 .1 8 1 0
-0 .0 4 5 6
0.3 5 9 4
4 .8 (5 )
C21
-0 .1 7 5 6
0.0456
0.3127
5 .6 (5 )
C22
-0 .0 5 6 3
0.1 3 1 2
0.3020
4 .8 (5 )
0.1337
0.0301
0.4107
6.0
-0 .0 7 1 1
-0 .1 1 6 8
0.4 2 9 0
6.0
HI 8 ***
HI 9
vo
U)
TABLE V III.
(C o n tin u e d )
Atom
Phenyl Ring C**
H20
x ( 10 ^ ct)
y ( 10 ^ ct)
z CIO4 cr)
B (10 ct)
■0.2666
-0 .1 0 7 0
0.3671
6.0
H21
■0.2572
0 .0 4 9 8
0 .2868
6.0
H22
■0.0524
0.1967
0.2685
6 .0
Phenyl Ring D**
0.2 0 9 9
(7 )
0.0187
(7 )
-0 .0 0 5 2
(5 )
2 .5 (2 )
C23
0.3029
0 .0 5 1 4
0.0651
1 .2 (3 )
C24
0.2 5 7 0
-0 .0 6 0 7
0.0247
2 .8 (4)
C25
0.1639
-0 .0 9 3 4
-0 .0 4 5 6
4 .0 (4 )
C26
0 .1 1 6 8
-0 .0 1 4 0
-0 .0 7 5 6
3 .9 (4 )
C27
0 .1 6 2 8
0.0981
-0 .0 3 5 2
4 .7 (5 )
C28
0.2558
0.1 3 0 8
0.0351
6 .0 (5 )
H24***
0 .2 9 0 8
-0 .1 1 7 6
0.0462
6. 0
H25
0 .1310
-0 .1 7 3 9
-0 .0 7 4 6
6.0
VO
TABLE V III.
(C ontinued)
Atom
P henyl Ring D**
H26
x (104 a)
y (104 ct)
(104 a)
B (10 ct)
0.0501
-0 .0 3 7 5
-0 .1 2 6 1
6 .0
H27
0.1 2 9 0
0.1 5 5 0
-0 .0 5 6 7
6 .0
H28
0.2 8 8 8
0.2113
0 .0 6 4 1
6 .0
P h en y l R ing B**
0.6888
( 8)
0 .2 8 7 4
(7 )
0 .1 2 1 1
( 5)
1 .8 (2)
C29
0 .5 7 2 5
0 .2 0 1 8
0 .1 3 5 9
2 .4 (4 )
C30
0.5810
0.2380
0 .0 5 9 2
3 .3 (4)
C31
0 .6 9 7 2
0.3237
0 .0 4 4 4
4 .5 (4 )
C32
0.8050
0.3 7 3 1
0 .1 0 6 4
5 . 8 (5 )
C33
0 .7966
0 .3 3 6 8
0 .1831
5 .4 (5 )
C34
0 .6803
0.2 5 1 2
0 .1 9 7 8
4 .0 (4 )
H30***
0 .5 0 3 6
0.2 0 2 6
0.0 1 4 7
6 .0
H31
0 .7 0 3 3
0.3497
-0 .0 1 0 6
6 .0
VO
in
TABLE V III.
(Continued)
Atom
Phenyl Ring E**
H32
x (10^
a)
y (10^ ct)
z CIO4 ct)
B (10 ct)
0.8 8 8 5
0.4346
0 .0 9 5 8
6 .0
H33
0.8 7 3 9
0 .3 7 2 3
0 .2 2 7 5
6 .0
H34
0.6 7 4 2
0.2 2 5 2
0 .2529
6 .0
Phenyl Ring F**
0 .4 8 6 6
(7 )
'- 0 .1 1 9 8
(7)
0.2 0 6 6
(5 )
2 .7 ( 2 )
-0 .0 2 4 3
0.1866
C36
0.4217
-0 .0 8 0 9
0.2538
3 .1 (5 )
C37
0.4481
-0 .1 7 6 4
0.2738
C38
0.5 1 3 0
-0 .2 1 5 3
0 .2 2 6 6
4 .7 (5 )
C39
0.5516
-0 .1 5 8 7
0 .1 5 9 4
4 .8 (5 )
C40
0.5252
-0 .0 6 3 2
0 .1 3 9 4
3 .3 (4 )
H36***
0.3751
-0 .0 5 3 0
0 .2 8 7 6
6 .0
H37
0 .4 2 0 4
-0 .2 1 7 0
0.3220
6 .0
•
00
0.4602
•
H
00
C35
(4 )
( 6)
to
O'
TABLE V III.
(Continued)
Atom
Phenyl Ring F**
H38
x (104 ct)
y CIO4
z CIO4 ct)
B (10 ct)
0.5320
-0 .2 8 3 9
0.2409
6. 0
H39
0.5982
-0 .1 8 6 6
0.1255
6.0
H40
0.5528-
-0 .0 2 2 6
0.0911
6.0
0.5000
0.5 0 0 0
0.0000
4 .8 (4 )
C41
0.5545
0.5 1 6 5
-0 .0 6 8 6
4 .0
C42
0 .4 2 0 6
0.4 5 8 9
-0 .0 7 5 5
4 .0
C43
0.3662
0 .4 4 2 4
-0 .0 0 6 9
4 .0
C44
0 .4 4 5 5
0 .4 8 3 5
0.0686
4 .0
C45
0 .5 7 9 4
0.5 4 1 1
0.0755
4 .0
C46
0 .6 3 3 8
0.5 5 7 6
0.0 0 6 9
4 .0
H41***
0 .5 9 3 5
0.5 2 8 3
-0 .1 1 7 9
6.0
Benaene
si
TABLE V III.
(C ontinued)
Atom
x
<104
ct)
y
(10
z ( 104 a)
4 a)
B (10 cr)
Benzene
H42
0 .3636
0 .4 2 9 4
-0 .1 2 9 7
6 .0
H43
0 .2 7 0 1
0 .4 0 1 1
-0 .0 1 1 9
6 .0
H44
0 .4 0 6 5
0 .4717
0.1179
6 .0
H45
0 .6 3 6 4
0.5 7 0 6
0.1297
6 .0
H46
0.7299
0.5 9 8 9
0.0119
6 .0
^ A n is o tro p ic th e rm a l p a ra m e te rs c a lc u la t e d f o r th e s e atom s w ith t h e i r s ta n d a rd d e v ia t i o n
g iv e n in p a r e n t h e s i s . T h is th e rm a l c o r r e c t i o n ta k e s th e form ,
exp ( - ( h 2P l l + k \
Atom
105
Ir
877
PI
P2
2 + i 2 P33 + 2 (h k p 12 + hjfcU13+ u p 23) ) )
•
1 0 5 fs22
1°
(9 )
944
(9 )
261
(3 )
341
( 6)
90
(3 )
-9
(3 )
1248
(74)
900
(59)
280
(22)
341
(53)
152
(32)
-5 8
(27)
832
(62)
877
(59)
328
(22)
237
(49)
82
(30)
72
(27)
h i
P33
105
P l2
1 0 5 P13
io
p23
vo
00
TABLE V III.
(F o o tn o tes Continued)
( A n is tr o p ic M odel)
Atom
105
Ir
875
(9 )
937
(9 )
261
(3 )
336
( 6)
89
(3 )
-12
(3 )
PI
1230
(73)
879
(60)
273
(22)
351
(53)
152
(31)
-55
(27)
P2
849
(62)
874
(59)
338
(23)
244
(49)
89
(3 0 )
76
(27)
h i
105
*22
105
P33
105
*12
105
*13
i o 5 b23
N1
2840 (344)
1538 (235)
257
(65)
1525 (253)
287 (116)
-2 4 (103)
M2
1753 (257)
1094 (237)
758 ( 1 2 0 )
230 (194)
138 (149)
304 (125)
M3
6204 (850)
3437 (471)
1711 (249)
-2820 (513)
3027 (422)
-1573 (263)
Cl
2189 (382)
1136 (269)
(2 9 )
288 (146)
179 (136)
C2
2074 (326)
931 (285)
459 (129)
744 (242)
27 (171)
-69 (154)
C3
2886 (555)
2196 (412)
790 (153)
-1 0 9 5 (367)
1074 (251)
-505 (183)
C4
1328 (280)
353 (226)
505 ( 1 1 1 )
77 (209)
-7 2 (209)
-2 8 5 (132)
275
(90)
966
**The o r i g i n o f th e p h enyl r in g s was p la c e d a t th e c e n te r and i n th e p la n e o f th e r i n g s .
The te m p e ra tu re f a c t o r s (B) r e p o r te d a re th e o v e r a l l B o f th e r i n g and th e i n d i v i d u a l l y
v a r r i e d a to m ic B. The a c t u a l B f o r e a c h atom o f th e r i n g i s th e sum o f th e s e two v a l u e s .
***The p o s i t i o n o f th e hyd ro g en atoms was c a lc u la te d u s in g 1 .0 0 X a s th e carb o n t o
h y d ro g en bond d i s t a n c e .
TABLE EC.
E u l e r i a n R o ta tio n A n g le s F o r The R ig id Groups I n
[lr(T C M )(C O )(P Ph3) 2 ] • h C6 H6
TABLE IX
E u l e r i a n R o ta tio n A n g le s (D e g re e s ) F o r th e R ig id G ro u p s I n
The M o le c u le , [lr(T C M )(C O )(P P h 3 ) 2 3-% CgHg.
G roup
P h i (1 0 a )
J i s o r d e r e d Model . .
■
T h e ta (IO ct)
Rho (1 0 a)
•
Phenyl A
2 9 .1
(9 )
6 0 .9
(4 )
8 8 .3
(9 )
Phenyl B
- 9 0 .3
(4 )
- 1 1 .0
(4 )
- 1 0 6 .1
(4 )
Phenyl C
- 1 2 8 .9
(5 )
3 4 .8
(4 )
- 9 .0
(5 )
Phenyl D
-1 5 4 .0
(4 )
-4 .2
(4 )
5 7 .6
(4 )
8 3 .6 (1 3 )
- 7 3 .2
(4 )
3 7 .7 (1 3 )
5 2 .2
(4 )
Phenyl E
Phenyl F
1 0 5 .8
C a rb o n y l
1 0 3 .8
7 9 .3 (2 3 )
1 4 3 .0 (1 5 )
Cyano 83
9 6 .2
1 1 9 .0 (3 0 )
1 1 6 .2 (2 7 )
Cyano 93
1 7 4 .4
1 3 4 .1 (3 3 )
- 1 1 2 .9 (3 4 )
B enzene
- 6 0 .5
A n is o tr o p ic M odel .
Phfenyl A
*
•
(7 )
-1 5 7 .7
(7 )
( 8)
- 1 4 5 .3
(7 )
9 4 .0
( 8)
2 8 .6 ( 1 0 )
6 0 .6
(4 )
8 8 .8
(9 )
•
Phenyl B
- 9 0 .5
(4 )
- 1 1 .1
(4 )
-1 0 6 .1
(4 )
Phenyl C
- 1 2 9 .0
(5 )
3 4 .8
(4 )
-8 .9
(5 )
Phenyl D
- 1 5 4 .0
(4 )
- 4 .1
(4 )
5 7 .4
(4 )
8 2 .9 (1 3 )
- 7 3 .1
(4 )
3 7 .3 (1 3 )
5 2 .1
(4 )
Phenyl E
Phenyl F
1 0 5 .5
C a rb o n y l
1 0 3 .8
B enzene
- 6 0 .3
(7 )
7 9 .0 (2 3 )
( 8)
- 1 4 5 .3
(7 )
- 1 5 7 .1
(7 )
1 4 3 .7 (1 5 )
9 4 .2
( 8)
TABLE X.
The O bserved And C a lc u la te d S t r u c t u r e F a c to r s F o r
[lr(T C M )(C 0 )(F P h 3 ) 2 ] - k C6 H6
103
*
•
II
11
11
1*
-1
I
*
T
•0
■
-9
•
•1 *
19
• II
I
>It
II
• 11
11
|4
••
II
•4
-•
•I
1
-T
f
-•
-*
•
• II
II
-11
II
11
11
•1 1
1*
II
• II
•
*
—4
I
•4
1
•1 1
II
•It
It
-I*
14
II
I
1
I
t
3
-*
*4
•I
1
I
-I
-r
r
■
“4
•4
t
II
•11
II
11
11
•1*
II
•1
1
•t
•*
-J
1
*4
-1
-1
-*
-7
-7
—
A
-4
-4
•II
-II
•It
It
• 1J
•II
1
-I
I
—
4
4
I
-«
TTT*T
-1
-II
11
It
11
•14
I
1
1
•1
«
4
NT
• 71
••1
141
*14
44*
l* t
41*
IM
441
4J«
441
•IB
• *1
*11
•74
1117
Ml
•43
441
701
in
in
417
lit
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TABLE XI
Bond L e n g th s And A ngles Found F o r The D is o rd e re d And
A n i s t r o p i c M odels o f [Ir(TC M ) (CO) ( P P h ^ j! ) * h c gHg
TABLE XX.
Bond L e n g th s (A n g stro m s) and Bond A n g le s (D e g re e s ) F o r th e
Compound, [ir(TCM)(CO)(PPh^)^] • % C5 H5 *
(a )
Bond
D is o rd e re d M odel
A n i s o tr o p i c Model
Ir-P l
2 .3 3 2
(7 )
2 .3 3 3
(7 )
Ir-P 2
2 .3 2 8
(6 )
2 .3 2 8
( 6)
Ir-N l
1 .9 8 5 (1 3 )
2 .0 0 0
(17)
Ir-C O
C0-01
1 .7 1 6 (1 6 )
1 .1 6 0 *
1 .7 3 1 (17)
1 .1 6 0 *
N l-C l
1 .1 7 3 ( 2 2 )
1 .2 3 2 (29)
N2-C2
1 .1 3 4 (2 8 )
1 .1 5 2 (36)
N3-C3
1 .1 6 0
*
1 .1 6 0
*
1 .1 0 2
(50)
C1-C4
1 .3 9 3 (2 3 )
1 .3 5 4 (30)
C2-C4
1 .3 2 1 (2 8 )
1 .2 6 2 (37)
C3-C4
1 .3 9 2 (4 8 )
1 .3 8 8 (39)
1 .4 4 8 (4 1 )
P1-C5
1 .8 0 3 ( 1 2 )
1 .8 0 3 (13)
P l-C ll
1 .8 2 8
(9)
1 .8 2 1
(9)
P1-C17
1 .8 1 8
(9)
1 .8 1 7
(9)
P2-C23
1 .8 2 1
(9)
1 .8 2 1
(9)
P2-C29
1 .8 4 4
(9)
1 .8 4 1
(9)
P2-C35
1 .7 9 9 ( 1 2 )
*H eld C o n s ta n t D uring R e fin e m e n t.
1 .8 0 5 ( 1 2 )
ZABLE XI.
(C ontinued)
(b)
A ngle
D is o rd e re d Model
A n is o t r o p ic Model
P l-Ir-P 2
1 7 2 .7
(4 )
1 7 2 .7
( 2J
P l- Ir- C O
8 8 .6
(9 )
8 8 .9
(9)
P l-Ir-N l
9 2 .0
( 6)
9 1 .7
(7 )
P 2 - Ir-C 0
9 2 .9
(5 )
9 2 .5
(9)
P 2 -Ir-N l
8 6 .1
(5 )
8 6 .5
(7 )
C O -Ir-N l
1 7 6 .8
(9 )
1 7 6 .6
(9)
Ir-C O -01
1 7 9 .0 (26)
1 7 9 .2 (27)
I r - N l- C l
1 7 5 .9 (19)
1 7 3 .0 (23)
C4-C1-N1
1 7 3 .3 (21)
1 7 6 .3 (22)
C4-C2-N2
1 7 9 .0 (1 8 )
1 7 6 .0 (25)
C4-C3-N3
1 6 9 .6 (51)
1 7 8 .2 (28)
1 7 4 .6 (51)
—
C1-C4-C2
1 2 3 .6 (1 7 )
1 1 9 .6 (22)
C1-C4-C3
1 1 5 .6 (23)
1 2 1 .1 (2 3 )
1 2 0 .6 (19)
—
1 1 8 .8 (19)
1 1 9 .3 (20)
1 1 2 .2 (21)
—
C2-C4-C3
C 3-C 4-C 3'
3 4 .5 (28)
- -
TABLE X II.
L e a s t- S q u a r e s P la n e s D eterm in ed F o r
[lr(T C M )(C O )(P Fh3) 2 ] • h C&H6
TABLE X II.
L e a s t- s q u a r e s p l a n e s ; th e a n g le ( I n d e g re e s ) b e tw e e n t h e i r
n o rm als and th e p e r p e n d ic u la r d i s t a n c e o f s e l e c te d atom s from t h e s e
p la n e s .
The e q u a tio n I s o f th e fo rm , Ax + By + Cz = D, w here x ,
y and z a r e e x p re s s e d i n f r a c t i o n a l c o o r d in a t e s .
P la n e
A
B
C
D
(a ) D is o rd e re d Model . . . .
( 1)
Ir -P l- C O
- 5 .4 5 7
5 .8 5 4
- 1 3 .0 4 8
- 4 .1 0 3
( 2)
Ir-P l-N l
-5 .1 9 9
6 .3 0 4
- 1 3 .0 7 9
- 3 .9 5 4
(3 )
Ir-P 2 -C O
- 6 .5 7 3
6 .6 9 6
- 1 1 .5 9 6
- 3 .9 6 9
(4 )
Ir-P 2 -N l
- 6 .3 1 0
7 .1 2 4
- 1 1 .6 4 8
-3 .8 2 7
(5 )
C1-C2-C4-C83
- 7 .5 7 5
8 .6 7 1
- 9 .0 2 1
- 3 .5 7 4
(6)
C1-C2-C4-C93
- 9 .9 9 0
7 .8 9 9
- 5 .0 4 6
- 2 .8 2 9
(7 )
C1-C2-C83
-7 .2 3 2
8 .7 0 7
- 9 .4 3 0
- 3 .6 0 7
( 8)
C1-C2-C93
-1 0 .2 5 4
7 .7 2 6
- 4 .4 1 5
. - 2 .7 3 9
(9 )
Ir-P l-P 2 -C O -N l
- 5 .7 9 4
6 .7 4 4
- 1 2 .3 5 2
- 3 .8 8 6
- 5 .9 6 6
6 .3 9 4
- 1 2 .3 5 9
- 2 .8 7 2
( 1 0 ) P1-P2-CO-N1
(b ) A n is o tr o p ic Model
*
•
•
•
( U ) Ir -P l- C O
( 12) Ir -P l- N l
- 5 .4 5 8
5 .8 4 3
- 1 3 .0 5 1
- 4 .1 0 6
- 5 .1 9 9
6 .2 9 4
- 1 3 .0 8 3
- 3 .9 5 6
(13) I r -P 2 -C 0
- 6 .6 0 1
6 .7 0 3
- 1 1 .5 6 2
- 3 .9 6 8
(14) I r - P 2 - N l
-6 .3 3 6
7 .1 3 9
- 1 1 .6 1 4
- 3 .8 2 4
(15) C1-C2-C3-C4
-8 .6 5 7
8 .5 0 5
- 7 .4 8 2
- 3 .3 3 1
(16) C1-C2-C3
- 8 .6 7 0
8 .4 9 9
- 7 .4 6 4
- 3 .3 3 5
(17) I r - P l- P 2 - C 0 - N l
- 5 .7 9 4
6 .7 3 8
- 1 2 .3 5 6
- 3 .8 8 8
(18) P1-P2-C 0-N 1
- 5 .9 5 4
6 .4 3 8
- 1 2 .3 5 1
- 3 .8 5 4
T ab le XXI.
(C o n tin u ed )
D e v ia tio n s o f S e le c te d Atoms From P la n e s (D is ta n c e s i n 8 )
i t ora
(5 )
( 6)
(7 )
( 8)
( 10)
(15)
- 0 .1 3 8
Ir
0 .0 2 4
-0 .0 3 6
-0 .0 0 7
C2
0 .0 2 5
- 0 .0 3 4
-0 .0 0 7
- 0 .0 1 1
C3
0 .1 0 2
-0 .1 3 0
C93
C4
-0 .0 6 2
0 .0 8 6
- 0 .1 1 1
0 .1 5 0
0.017
0 .0 2 5
N1
0 .123
-0 .1 5 0
0 .1 2 4
- 0 .1 4 4
0 .0 3 8
0 .0 4 4
N2
0 .1 0 1
-0 .1 3 0
0 .0 9 6
- 0 .1 2 1
- 0 .0 0 1
0 .0 0 6
- 0 ,0 2 0
-0 .0 0 8
N3
N83
N93
(18)
-0 .1 4 2
Cl
C83
(16]
- 0 .0 7 2
0 .0 7 5
- 0 .2 0 1
- 0 .1 6 8
111
112
TABLE X l t .
(C o n tin u e d )
D ih e d r a l A n g le s ; A n g les B etw een P la n e s ( I n D e g re e s ).
P la n e
A ngle
P la n e
Angle
( 1 ,4 )
7 .6
( 1 1 ,1 4 )
7 .8
( 2 ,3 )
7 .9
( 1 2 ,1 3 )
8 .1
( 5 .9 )
1 4 .9
( 1 5 ,1 7 )
2 0 .6
( 6 .9 )
3 0 .3
DISCUSSION
C o o r d in a tio n a b o u t I r ;
C o n s id e rin g th e m o le c u la r p la n e co n ­
t a i n i n g th e P1-P2-N 1-C 0 a to m s, t h e I r atom l i e s - 0 .1 3 8 and - 0 .1 4 2 8
o u t o f t h i s p la n e f o r th e d is o r d e r e d m odel (DISM) and a n i s o t r o p i c
m odel (ANIM) r e s p e c t i v e l y .
The g e n e r a l c o o r d in a ti o n a b o u t t h e I r
i s p l a n a r and can be s e e n i n F ig u r e 4 .
The tr ip h e n y lp h o s p h in e
g ro u p s a r e t r a n s t o e a c h o th e r and l i e 2 .3 3 2 (7 ) and 2 .3 2 8 ( 6 ) 8
from th e I r atom i n DISM.
I n t h e ANIM s t r u c t u r e th e y a r e q u i t e
co m p arab le a t 2 .3 3 3 (7 ) and 2 .3 2 8 ( 6 ) 8 .
W ith in e x p e r im e n ta l
e r r o r , th e s e l e n g th s a r e th e same a s th o s e r e p o r t e d f o r s i m i l a r
tr a n s s tr u c tu r e s i f irid iu m .
24 -3 1
The Ir-C O d i s t a n c e i s 1 .7 1 6 (1 6 )
f o r DISM and 1 .7 3 1 (1 7 ) 8 f o r ANIM.
T h ese b onds a r e among th e
s h o r t e s t r e p o r t e d f o r ir i d i u m c a r b o n y ls w h ic h ra n g e from 1 . 7 0 t o
1 .9 6 3 ^ 2 4 ,2 6 ,3 0 33
bond t r a n s t o th e c a r b o n y l i s 1 .9 8 5
(1 3 ) i n DISM and 2 .0 0 0 (1 7 ) i n ANIM.
E m p i r ic a ll y I r , Ru, and Os
a r e s i m i l a r i n t h e i r b o n d in g p r o p e r t i e s , b u t o n ly two s t r u c t u r e s
h a v e b e e n B tu d ie d by X -ray d i f f r a c t i o n w h ic h c o n t a i n sp h y b r id iz e d
n i t r o g e n s bound t o th e m e ta l. The f i r s t com plex i s
[ I r ( h 2 - TCNE) ( h 1 - TCNE) (CO) ( P P h ^ 2 ] 34
w here TCNE i s te tr a c y a n o e th y le n e and PPh^ i s tr i p h e n y lp h o s p h in e .
T h is com plex c o n ta i n s two TCNE g ro u p s bonded i n two s e p a r a t e w a y s:
FIGURE 4 .
The M o le c u la r C o n f ig u r a tio n Of
[Ir(TC M ) (CO)<PPh3) 2 ]* h C6 Hg
2
1
The h -TCNE i s bound v i a two M-C b o n d s and th e h -TCNE i s bound by
a k e te n e im in a to
(M-N) bond a t a d i s t a n c e o f 2 .0 2 4 ( 8 ) 8 , c o n s id e re d
by th e a u th o r s o f th e s t r u c t u r a l r e p o r t t o be a s i n g l e M-N bond.
qe
The o n ly o th e r s t r u c t u r e r e p o r te d i s [Ru(NH^)^NgRuCNH^)
The c a t i o n n o t o n ly c o n t a i n s sp
3
h y b r id i z e d n it r o g e n s b u t a l s o an
sp h y b r id iz e d d i n i t r o g e n l i n e a r l y b r id g i n g th e m e ta ls w ith e q u a l
Ru-N d i s t a n c e s o f 1 .9 2 8 ( 6 )
I t sh o u ld b e n o te d t h a t in th e
d i n i t r o g e n lig a n d , th e N-N bond l e n g t h i s 1 .1 2 4 (1 5 ) X w h ic h ,
o36
th o u g h n o t s i g n i f i c a n t l y lo n g e r th a n th e N-N bond o f 1.097 (2 ) A
found i n th e f r e e d i n l t r o g e n m o le c u le , s t i l l s u g g e s ts t h a t t h e r e
may be
some d o n a tio n o f e l e c t r o n s fro m th e
m e ta l o r b i t a l s i n t o
th e ti*
s y ste m o f th e d i n i t r o g e n lig a n d and
a Ru-N bond o f o r d e r
g r e a t e r th a n 1 .0 .
Based on th e r e s u l t s o f th e s e two s t r u c t u r a l
s t u d i e s , i t i s c o n c lu d e d t h a t th e m e t a l - n i t r o g e n bond o r d e r I n
th e p r e s e n t s t r u c t u r e i s v e r y n e a r l y 1 . 0 .
A d d itio n a l
t h e p r e s e n t compound
e v id e n c e f o r th e I r -N bond o r d e r o f 1 .0 i n
l i e s i n th e f a c t t h a t
th e mean p la n e o f th e
TCM m o le c u le i s t i l t e d w i t h r e s p e c t t o th e mean m o le c u la r p la n e
by a n a v e ra g e o f 2 2 . 6 and 2 0 . 6 ° i n th e two r e s p e c t i v e m odels
(T a b le X I I ) .
T h is d e v i a t i o n from c o - p l a n a r i t y d e c r e a s e s th e e x ­
t e n t o f o v e r la p o f th e TCM m o le c u la r n * o r b i t a l s w i t h th e d
o r b i t a l s o f th e m e ta l and t h e r e f o r e d im in is h e s t h e e f f e c t i v e b ack
d o n a tio n o f e l e c t r o n s fro m th e m e ta l t o th e TCM a n tib o n d in g sy ste m .
B onding i n t r i p h e n y lp h o s p h in e :
The l e n g th s o f th e P-C
bonds i n t h e tr ip h e n y lp h o s p h in e lig a n d s ra n g e fro m 1 .7 9 9 (1 2 ) t o
1 .8 4 4 (9 ) X (a v e ra g e o f 1 .8 1 9 (1 0 ) X) f o r DISM and 1 .8 0 3 (1 3 ) to
1 .8 4 1 (9 ) S (a v e ra g e o f 1 .8 1 8 (10) 8 ) f o r AN3M.
Even th o u g h th e
i n d i v i d u a l v a lu e s a r e n o t s i g n i f i c a n t l y d i f f e r e n t from th e
a v e ra g e v a lu e o f 1 .8 2 8 (5 ) X r e p o r t e d f o r th e tr ip h e n y lp h o s p h in e
37
m o le c u le ,
t h e r e a p p e a r s to be m a rg in a l s i g n i f i c a n c e in th e
h ig h e s t and lo w e s t v a lu e s r e p o r t e d .
The r e a s o n f o r t h i s d i f f e r e n c e
i s p o s t u l a t e d t o be d u e t o p a c k in g o f t h e m o le c u le s in th e s o l i d
s t a t e r a t h e r th a n a n y s i g n i f i c a n t e l e c t r o n i c d i s t o r t i o n .
S in c e
th e p h e n y l g ro u p s w ere t r e a t e d a s r i g i d h ex ag o n s th ro u g h o u t r e ­
fin e m e n t, t h e C-C bond l e n g t h was h e ld i n v a r i a n t a t a v a lu e o f
1 .3 9 * I 3 8 ' 4 0
B onding in TCM:
F ig u r e 6 i s a summary o f bond le n g th s
and a n g le s found f o r t h e d is o r d e r e d and i s o t r o p i c m o d els o f th e
TCM g ro u p .
D is c u s s io n o f th e bond le n g th s i n t h i s s t r u c t u r e m u st
be a p p ro a c h e d w ith c a u t i o n b e c a u se o f th e l a r g e s ta n d a r d d e v i a t i o n
a s s o c ia te d w ith each v a lu e .
Two f a c t o r s w hich c o n t r i b u t e t o th e
l a r g e e r r o r s a r e th e h e av y atom e f f e c t and th e d is o r d e r e d cyano
g ro u p .
The p re s e n c e o f a h eav y atom ( I r , 77 e l e c t r o n s ) i n th e
v i c i n i t y o f l i g h t atom s (Cf 6 , and N,7 e l e c t r o n s ) r e s u l t s i n l a r g e
u n c e r t a i n t i e s in th e p o s i t i o n s o f th e l i g h t atom s w h ic h a r e r e f l e c ­
te d i n t h e bond le n g th s o f th e l i g h t a to m s.
The seco n d o f th e s e
FIGURE 5.
End On View Of The D is o rd e re d And I s o t r o p i c
M odels F o r
[ir(T C M ) (CO) (P P h3) 2 ] . h C6 H6
DISORDERED MODEL
ANISOTROPIC MODEL
FIGURE 6.
A Summary Of Bond L e n g th s And A ng les D is p la y e d
I n The D is o r d e r e d And A n i s o t r o p i c Models Of
[ir(TC M )(C O )(PPh3) 2 3 - % C6 H6
N93
N83
\
\
1.16
C83
1.16
C93
1.39
1.45
116
o
119
1.39
1.17
Nl
o
112
C4
1.32
121
1.39
Cl
1.17
Nl —
124
C2
C2
t
1.13
1.13
N2
N2
DISORDERED MODELS
121
Nl
1.35
1.23
/ 1.26 i20°
C2
/
1.15
N2
ANfSOTROPIC MODEL
122
123
f a c t o r s , th e d is o rd e re d g roup, a ls o cau ses u n r e l i a b i l i t y in th e
a to m ic p o s i t i o n s b u t t o a much g r e a t e r e x t e n t t h a n t h a t o f th e
heav y atom e f f e c t .
B ecause o f t h e s e l a r g e d e v i a t i o n s , no
d e f i n i t i v e s t a t e m e n t can b e made a b o u t t h e l e n g t h s o f t h e s e b o n d s.
However, a g e n e r a l t r e n d was n o te d i n t h e shape o f t h e I n d i v i d u a l
m o d e ls .
The v a l u e s i n T a b le X II i n d i c a t e t h a t i n ANIM model t h e
TCM m o le c u le i s a p p a r e n t l y p l a n a r .
B u t, i n one o f t h e DISM
m od els t h e n i t r o g e n atom s l i e above t h e C1-C2-C4-C83 p l a n e (N l, 0 . 1 2 3 ;
N2, 0 . 1 0 1 ;
N83, 0 .0 7 5
(C4, - 0 . 0 6 2 8 ) .
and th e C4 atom l i e s below t h i s p la n e
I n th e o t h e r d i s o r d e r e d m o d el, t h e n i t r o g e n
atom s l i e below t h e C1-C2-C4-C93 p la n e (N l, - 0 . 1 5 0 ; N2, - 0 . 1 3 0 ;
N93, - 0 . 2 0 1 X) w h i l e t h e C4 atom l i e s above t h e p la n e (C4, 0 .0 8 6
S ).
T hu s, i n t h e ANIM m odel th e TCM l i g a n d a p p e a r s p l a n a r w h ile
th e DISM s t r u c t u r e can b e view ed a s two n e a r l y c o i n c i d e n t TCM
h a l f m o le c u le s b o th o f w h ic h te n d to w ard t e t r a h e d r a l c o n f i g u r a t i o n s .
The e n d - o n v ie w o f t h e TCM i n F ig u r e 5 d i s p l a y s t h e s e a r r a n g e m e n ts .
In o r d e r t o u n d e r s t a n d t h e r a t i o n a l e b e h in d t h e DISM and
ANIM m o d e ls , a b a s i c v a l e n c e bond a p p r o a c h t o t h e Ir-TCM b o n d in g
may be u s e d .
T h e re a r e f i v e
drawn and a r e v i s u a l i z e d a s ,
Lewis
s t r u c t u r e s t h a t c an be
(2 )
—
Ir
N
,CN
I
©
I
( 3 ')
0
G \,
----- I'
r—©
V = C —1
I
M
I© ©
R= r C=
C
I r? =
(4)
V “
/®
CN
S in c e t h e I r - N bond d i s t a n c e h a s b e e n e s t a b l i s h e d a s e s s e n t i a l l y
a s i n g l e b o n d , s t r u c t u r e (4 ) c o n t r i b u t e s t h e l e a s t o f t h e
Lew is f o r m s .
In s tru c tu re
(2 ) t h e Ir -N -C a n g l e would be e x p e c te d
t o d i f f e r s i g n i f i c a n t l y from 1 8 0 ° i f t h i s fo rm w ere a m a jo r c o n t r i b u t e r to th e t o t a l s t r u c t u r e .
The a n g l e s fo u n d i n t h e p r e s e n t
compound a r e 1 7 5 .9 ( 1 9 ) ° f o r DISM and 1 7 3 .0 ( 2 3 ) ° f o r ANIM w h ic h
in d ic a te s th a t s tru c tu re ( 2) does not c o n trib u te e x te n s iv e ly to
th e o v e ra ll e le c tro n ic s tr u c tu r e .
Form ( 1 ) o f t h e f i v e i s m ost
l i k e l y t h e l a r g e s t c o n t r i b u t o r o f a l l th e
t h e t r u e b o n d in g schem e.
L ew is
s t r u c t u r e s to
The I r - N l - C l a n g l e w ould be n e a r 180°
and t h e TCM g ro u p w ould d i s p l a y t r i g o n a l p l a n a r symmetry.
The
a n i s t r o p i c model c e r t a i n l y d i s p l a y s t h e 180° a n g le and t r i g o n a l
p l a n a r symmetry, b u t t h i s form c a n n o t e x p l a i n t h e h ig h t h e r m a l
m o tio n d i s p l a y e d by C3N3.
I f we c o n s i d e r some c o n t r i b u t i o n from
(3) and ( 3 f ) t o t h e t o t a l form , we can e x p l a i n t h e ANIM and DISM
stru c tu re s.
I n t h e DISM s t r u c t u r e , i t was p o i n t e d o u t t h a t t h e
TCM g r o u p s d e f in e d by t h e two d i s o r d e r e d m od els a r e p u c k e re d i n
o p p o site d ir e c tio n s .
Forms (3) and ( 3 1) a r e a l s o p u c k e r e d i n op­
p o s i t e d i r e c t i o n s and form a t e t r a h e d r a l a r ra n g e m e n t a b o u t t h e
c e n t r a l carbon.
The c o n t r i b u t i o n o f t h e s e two forms i s l e s s th a n
form ( 1 ) s i n c e th e TCM g ro u p shows o n ly a s l i g h t d e f o r m a t i o n from
p la n a rity .
T h is s t r u c t u r e would r e p r e s e n t a t r u e l y d i s o r d e r e d
model w h e re h a l f t h e m o le c u le s i n t h e c r y s t a l would be d i s t o r t e d
in one d i r e c t i o n w h i l e th e r e m a in in g m o le c u le s would be d i s t o r t e d
i n th e o p p o s i t e d i r e c t i o n .
F o r t h e ANIM m o d e l, t h e r e a r e two p o s s i b l e e x p l a n a t i o n s
t h a t n o t o n ly a c c o u n t f o r t h e n e a r l y p l a n a r s t r u c t u r e o b s e r v e d f o r
th e TCM l i g a n d b u t a l s o t h e a p p a r e n t l y h i g h th e r m a l m o tio n o f th e
C3N3 c y an o g ro up .
I f we assume t h e s t a t i c d i s o r d e r , DISM, i s th e
c o r r e c t m odel, th e n t h e a v e r a g e p o s i t i o n o f t h e d i s o r d e r e d gro up s
would g i v e r i s e t o a t r i g o n a l p l a n a r c o n f i g u r a t i o n , and t h e C3N3
group w ould a l s o a p p e a r t o e x h i b i t h ig h t h e r m a l m o tio n i n a t t e m p t i n g
t o a c c o u n t f o r th e e l e c t r o n d e n s i t y i n t h a t r e g i o n .
The o t h e r
p o s s i b i l i t y i s t h a t t h e two forms a r e i n a dynam ic e q u i l i b r i u m
s i m i l a r t o th e u m b r e lla i n v e r s i o n i n t h e NH^ m o le c u le .
T h is
dynamic d i s o r d e r would a f f e c t o n l y th e C3N3 u n i t s i n c e t h i s cyano
g ro u p i s s i t u a t e d i n a c a v i t y c r e a t e d b y t h e p a c k in g o f m o le c u le s
in th e s o lid s t a t e
( F ig u r e 7 ) .
The C2N2 cyano g ro u p
is le ss fre e
t o o s c i l l a t e b e c a u s e o f t h e l a c k o f s p a c e s u r r o u n d in g i t s p o s i t i o n .
From t h e d i f f r a c t i o n d a t a we c a n n o t t e l l w h e th e r t h e s t a t i c d i s ­
o r d e r or' t h e dynam ic i n v e r s i o n model d e p i c t s t h e a c t u a l p h y s i c a l
s itu a tio n , but i t
i s c l e a r t h a t th e f i v e
Lewis
fo rm s c o n t r i ­
b u te t o t h e o v e r a l l s t r u c t u r e i n th e o r d e r
(1 ) > (3) = ( 3 ' )
T h e re fo re , th e d i f f r a c t i o n d a ta
»
(2 ) > ( 4 ) .
and b o t h r e f i n e m e n t m o dels a r e
c o n s i s t e n t w i t h a n o n - p l a n a r TCM g ro u p .
I t c a n be c o n c lu d e d from t h e above d i s c u s s i o n t h a t form
( 1 ) i s t h e e x c l u s i v e c o n t r i b u t o r t o t h e p o ly m e r ic s t r u c t u r e s o f
t h e i o n i c s a l t M(TCM)n w here M = Na+, K+, Cu44", and Ag+, ^ r
i n w hich t h e TCM a n i o n i s r e p o r t e d t o be
p la n a r.
^
Enemark and
Holm h ave p e rfo rm e d m o l e c u l a r o r b i t a l c a l c u l a t i o n s f o r t h e D_.
3n
c o n f i g u r a t i o n o f t h e TCM a n i o n and fo u n d t h a t t h e n e g a t i v e c h a rg e
r e s i d e s e q u a l l y on t h e e q u i v a l e n t n i t r o g e n a to m s,
8
but in
Ir(TCM)(CO)(PPh ^ ) 2 t h e n i t r o g e n atoms a r e no lo n g e r e q u i v a l e n t and
some c o n t r i b u t i o n from form s (3 ) and ( 3 ’ ) i s e x p e c te d t o t h e
o v e r a l l s t r u c t u r e , t h u s i n t r o d u c i n g a d e f o r m a t i o n from p l a n a r i t y .
C o n clu sio n s:
B a d d le y and L e n a rd a r e p o r t e d t h e s tu d y o f
s e v e r a l d ic y a n o k e t e n i m i n a t o com plexes o f some n o b le m e t a l s and
FIGURE 7 .
A P a c k in g Diagram o f M o le c u le s F o r
[Ir(TCM) (CO) (PPh3) 2 ] . % C6 H6
among t h e s e was t h e Ir(TCM )(CO)(PPh 3) 2 com plex.
14
They r e p o r t e d
a v a l u e o f 2005 cnT* f o r t h e CO s t r e t c h i n g f r e q u e n c y and p r e d i c t e d
e ls ste re o -c h e m istry .
b a se d on
The p r e d i c t i o n o f t h e c i s a rra n g e m e n t was
nmr s p e c t r a o f Ir(TCM) (CO) (PMePh^Jj o b t a i n e d from
Ir(T C M )(C O )(P P h^^* and on t h e c r i t e r i o n o f Kemmit and B l a n d . ^
Kemmit and Bland c o n c lu d e d from e m p i r i c a l o b s e r v a t i o n s t h a t i n
p l a n a r com plexes o f p la t i n u m , i r i d i u m , and rh odium , when th e
h i g h e r e n e r g y band o f th e two PPh^ i n f r a r e d b an d s i n t h e r e g i o n
-1
o f 1570-1590 cm
was g r e a t e r i n i n t e n s i t y , c i s s t e r e o c h e m i s t r y
was fo u n d .
When t h i s s t u d y r e v e a l e d th e t r a n s c o n f i g u r a t i o n o f
Ir(TCM) (CO) (PPh3) 2 , a n a p p a r e n t c o n f l i c t a r o s e b e tw e e n i n f r a r e d
and NMR d a t a , w h ic h p r e d i c t e d t h e c i s a r r a n g e m e n t, and X -ra y
d i f f r a c t i o n d a t a w h ic h c l e a r l y showed t h e t r a n s s t r u c t u r e .
t h e r e was n o t enough sample re m a in in g from t h e
S ince
re c ry sta lliz e d
I r compound u sed i n t h e d i f f r a c t i o n s tu d y , no i n f r a r e d d a t a could
be c o m p ile d .
The o n l y a l t e r n a t i v e was t o r e s y n t h e s i z e th e com14
pound u s i n g t h e method o f B ad d ley and L e n a rd a .
T h i s was done by M rs.
D iane H. H a m ilto n , who i s a d o c t o r i a l c a n d i d a t e a t L o u i s i a n a S t a t e U ni­
v e r s i t y , B ato n Rouge, and t h e p r o d u c t was r e c r y s t a l l i z e d from d i c h l o r o m e th a n e /h e x a n e , and a n i n f r a r e d s p e c tru m was o b t a i n e d , (F ig u r e 9).
T h is
s p e c tru m was compared w i t h t h a t o f th e o r i g i n a l compound and was
fo un d t o ’ a g r e e w e l l .
-1
-1
The v(C ()w as found t o be 1993 cm
(1995 cm
a c c o r d i n g t o B ad d ley and L e n a rd a who i n a d v e r t e n t l y r e p o r t e d 2005 cm
FIGURE 8.
I n f r a r e d Spectrum F o r
c i s - [ Ir(TC M )(C O )(PPh^)2 ]
CIS-In(TCM)(CO)(PPh )
32
PPH
2220
CO (1993)
2180
2162
i
I
'
I
2300
'— I— i— I— i— I— i— |— i— |— i— |— i— |— I
2100
2200
1900
2000
1700
1800
1500
1600
FREQUENCY (CM-1) ----- >
and t h e two bands o f PPh^ (1570 - 1590 cm
c h e m i s tr y .
The n e x t s t e p was t o
in d ic a te d c is s te r e o ­
r e c r y s t a l l i z e t h i s compound from
benzene and hexane a s was done t o o b t a i n c r y s t a l s f o r th e p r e s e n t
d i f f r a c t i o n stu d y .
The r e s u l t s o f t h e I n f r a r e d s p e c tru m ( F i g u r e 9)
a r e q u i t e d i f f e r e n t from t h o s e o f th e o r i g i n a l compound.
The v (CO)
was s h i f t e d t o 1980 cm * and th e r e l a t i v e i n t e n s i t i e s o f t h e
bands i n d i c a t e d a t r a n s a rra n g e m e n t.
Form t h e s e i n f r a r e d d a t a i t
a p p e a r s t h a t th e c i s a rra n g e m e n t found b y B ad d ley and L en ard a had
b e en c o n v e r te d t o th e t r a n s s t r u c t u r e upon
r e c r y s t a l l i z a t i o n from
benzene and h e x a n e .
T h e re i s one r e m a in in g q u e s t i o n c o n c e r n in g t h e h ig h
-1
i n f r a r e d f r e q u e n c y f o r t h e c a r b o n y l a t 1980 cm
t r a n s compound.
i n th e p r e s e n t
For h a lo g e n s and p s e u d o h a lo g e n s o f th e form
tra n s -[ir(X X C O ) ( P P h ^ g ] (w here X i s C l, B r, I , and SCN) t h e i n ­
f r a r e d f r e q u e n c i e s a r e r e p o r t e d t o be 1950 ( C l ) , 1956 ( B r ) ,
- 1 41
1955 (X ), and 1971 (SCN) cm
.
i t becomes c l e a r t h a t the-
Lewis
From th e v a l e n c e bond a p p ro a c h
form s o f TCM t h a t c o n t r i b u t e
most t o t h e g e n e r a l s t r u c t u r e a r e i o n i c (weak sigma d o n o r s ) .
S in c e th e PPh^ and c a r b o n y l a r e known t o be weak e l e c t r o n d o n o r s ,
t h e r e a r e no l i g a n d s s u r r o u n d in g th e I r atom tfi a l l e v i a t e t h e
p o s i t i v e c h a r g e on t h i s c e n t r a l m e t a l .
B ecause o f t h i s r e s i d u a l
p o s i t i v e c h a r g e , th e I r i s e l e c t r o p h i l l i c and d o e s n o t r e a d i l y
ba ck d o n a te e l e c t r o n s i n t o t h e tt* sy ste m o f t h e c a r b o n y l s i n c e
t h i s would c r e a t e an e v e n l a r g e r p o s i t i v e c h a rg e on t h e m e t a l .
FIGURE 9.
I n f r a r e d Spectrum F o r
t r a n s - [ir(TCM )(CO)(PPh ) ]
TRANS - In(TCM)(CO)(PPh )
O
mm
PPh
2220
CO (1980)
2180 V 2160
2100
2300
2200
1900
2000
1700
1800
1500
1600
FREQUENCY (C M " ')----->
T h e r e f o r e , w i t h o u t t h e b a c k d o n a t i o n o f e l e c t r o n s from t h e m e ta l
^ o r b i t a l s i n t o t h e c a r b o n y l a n t i b o n d i n g sy ste m , l i t t l e w eak en in g
o f th e GO bond t a k e s p l a c e and t h e CO s t r e t c h i n g f r e q u e n c y i s
found a t a h i g h e r e n e r g y t h a n i n t h e c o r r e s p o n d i n g h a lo g e n compounds
w hich a p p a r e n t l y c o n t a i n more c o v a l e n t c h a r a c t e r i n t h e i r M - X
bond t h a n t h a t o f t h e TCH complex.
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W. R. B u sin g , K. 0. M a r tin and H. A. L evy, "0RFLS, A
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W. A. B enjam in, I n c . , New Y ork, 1969.
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D. M. P . M ingos, W. T. R obinson and J . A. I b e r s , I n o r g . Chem. .
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S. J .
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S. J .
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N. A. B a i l e y , C. J . J o n e s , B. L. Shaw and £ . S i n g l e t o n ,
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J . S.
R i c c i , J . A. I b e r s , J . Am. Chem. Soc. . 9 3 . 2 3 9 1 (1 9 7 1 ).
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I . M. T r e i t e l , M. T. B lo o d , R. E. Marsh and H. B. Gray,
J . Am. Chem. S o c . . 9 1 . 6 5 1 2 (1 9 6 9 ).
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L. E. S u t t o n e d . " I n t e r a t o m i c D i s t a n c e s S u pp lem en t" s p e c i a l
p u b l i c a t i o n 18, The Chemical S o c i e t y , London, 1965.
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J. J.
D a ly , J . Chem. Soc. . 3 7 9 9 (1 9 6 4 ).
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H. J .
M. Bowen, " T a b le s o f I n t e r a t o m i c D i s t a n c e s
and Con­
f i g u r a t i o n i n M o le c u le s and I o n s , " #11, Chem. S o c ., London,
1958.
39.
L. P a u l i n g , "The C hem ical B on d ," C o r n e l l U n i v e r s i t y P r e s s ,
I t h a c a , New York, 1967.
40.
C h em ical Rubber C o r p o r a t i o n (CRC), "Handbook o f C h em istry
and P h y s i c s , " 49. ( 1 9 6 8 ) .
41.
J . C h a t t , D. P. M e l v i l l e and R. L. R ic h a r d s , J . Chem. S o c . .
(A ), 2 8 4 1 (1 9 6 9 ).
42.
C. K. Jo h n so n , "ORTEP" P l o t t i n g Program , Oak R idge N a t i o n a l
L a b o r a t o r y , ( J u n e , 1 9 6 5 ).
CHAPTER I I I .
THE X-RAY STRUCTURE DETERMINATION
OF
TAMAULIPIN-A, Cl 5H2 ()0 3
139
INTRODUCTION
I n r e c e n t y e a r s , no m a jo r s u c c e s s h a s b e e n r e a l i z e d i n
th e f i e l d o f c a n c e r r e s e a r c h .
The compounds s y n t h e s i z e d i n
c h e m ic a l l a b o r a t o r i e s have met w i t h l i m i t e d s u c c e s s i n a r r e s t i n g
th e g ro w th i n c a n c e r o u s c e l l s .
T h e r e f o r e , a new a p p r o a c h i s
b e in g im p lem en ted , t h a t o f i s o l a t i n g from s e l e c t e d p l a n t s p e c i e s
n a t u r a l p r o d u c t s t h a t a r e known t o e x h i b i t a n t i l e u k e m i c and tum orin h ib ito ry c a p a b ilitie s .
1
N. H. F i s c h e r , L .S .U .- B .R . h a s s u c c e s s f u l l y i s o l a t e d
s e v e r a l compounds o f th e g e r m a c r a n o lid e c l a s s ( s e s q u i t e r p e n e
l a c t o n e s c o n t a i n i n g a 10 -membered c a r b o c y c l i c u n i t ) , some o f
w h ic h have b e e n shown t o e x h i b i t t h i s a n t i l e u k e m i c and turaorin h ib ito ry c a p a b ility .
2 3
*
One o f t h e s e compounds, T a m a u lip in -A ,
was i s o l a t e d from c e r t a i n M exican p o p u l a t i o n s o f t h e s p e c i e s
Ambrosia c o n f e r t i f l o r a DC.
2a
An e x t e n s i v e c h e m ic a l and s p e c t r a l
s t u d y o f th e a c e t a t e d e r i v a t i v e o f t h i s compound was u n d e r ta k e n by
F i s h e r et_ a l . and from nrar s p e c t r a l d a t a
2b
t h e y c o n c lu d e d t h a t i n
s o l u t i o n t h e two m e th y l g ro u p s e x h i b i t e d t h e svn o r i e n t a t i o n .
From a l i t e r a t u r e s e a r c h , i t a p p e a r s t h a t o n l y one x - r a y
s t u d y h a s b e en u n d e r ta k e n on a t r a n s . t r a n s - c y c l o d e c a - 1 , 5d ie n e g e r m a c r a n o lid e s e s q u i t e r p e n e , b u t t h i s was a h e a v y atom (Ag)
140
com plex.
4
T h e r e f o r e , T am a u lip in -A i s t h e f i r s t urtcomplexed
s t r u c t u r e o f t h i s t y p e t o be d e t e r m i n e d .
The s tu d y o f t h i s
s t r u c t u r e was u n d e r t a k e n f o r t h e d u a l p u rp o s e o f c o n f ir m i n g
t h e s t r u c t u r a l p r e d i c t i o n s o f F i s c h e r , and a l s o t o l e a r n th e
p r o c e s s o f d i r e c t m e th o d s.
CRYSTAL DATA
The p a l e y e l l o w c r y s t a l s o f T a m a u lip in -A , c i 5 H20°3 w ere
r e c r y s t a l l i z e d from a b s o l u t e e t h a n o l and a specim en 0 ,5 1 x 0 .4 2 x
0 .3 2 mm was u se d i n t h e d i f f r a c t i o n s tu d y .
The compound c r y s t a l l i z e s
i n th e o rth o r h o m b ic s y ste m w i t h u n i t c e l l d im e n s io n s o f £ = 7 .8 9 0
( 9 ) , b = 1 1 .9 5 7 ( 1 3 ) , c = 14 .6 49 (1 7 ) 55, V = 1382 8 3 , an d FQ0() = 536
e le c tro n s.
The d e n s i t y was d e te r m in e d by th e f l o a t a t i o n method
u s i n g an a q u eo u s s o l u t i o n o f sodium brom ide and found t o be 1 . 2 0
-3
g.cm . The c a l c u l a t e d d e n s i t y , a ssu m in g f o u r m o le c u le s p e r
-3
u n i t c e l l , i s 1 .1 9 g.cm .
The c r y s t a l used fo r data c o l l e c t i o n was bounded by
f a c e s b e lo n g in g th e th e forms { l0 0 } ,
[ 0 0 l3 ,
{ 0 1 0 }, and { O il} .
No a b s o r p t i o n c o r r e c t i o n was made s i n c e t h e c a l c u l a t e d l i n e a r
a b s o r p t i o n c o e f f i c i e n t (p, f o r 1 = 0 .7 1 0 7 £ ) was 0 .8 9 cm"'*’.
As­
suming a r a d i u s o f 0 .0 2 5 cm, t h i s r e s u l t s i n a (iRmax = 0 . 0 2 ,
w h ic h i n d i c a t e s t h a t a b s o r p t i o n d id n o t s i g n i f i c a n t l y a l t e r th e
in te n s ity d a ta .
B ecause o f t h e o r th o g o n a l u n i t c e l l c h o s e n , t h e p h o to g ­
r a p h y o f r e c i p r o c a l s p a c e was s i m p l i f i e d and s e v e r a l W e is s e n b e rg ,
p r e c e s s i o n , and cone a x i s p h o to g r a p h s w ere t a k e n .
The s y s t e m a t i c
a b s e n c e s d i s p l a y e d on t h e e m u ls io n f i l m s w ere hOO, h = 2n + 1;
OkO, k = 2n + 1 ; OOjJ> 1 s 2n + 1, and t h e s e a b s e n c e s u n iq u e ly
d e f i n e s p a c e group P2^2^2^ (D^, number 1 9 ) . ^
EXPERIMENTAL PROCEDURE
The c r y s t a l s o b ta in e d from t h e r e c r y s t a l l l z a t l o n o f t h e
compound w ere v e r y l a r g e .
A c r y s t a l o f s u i t a b l e s i z e was c u t
from one o f t h e l a r g e c r y s t a l s and examined c a r e f u l l y u n d e r a
p o l a r i z i n g m ic ro s c o p e f o r any i n d i c a t i o n o f t w in n in g .
The s p ec im e n
a p p e a re d t o b e a good s i n g l e c r y s t a l a n d , t h e r e f o r e , a s e r i e s o f
p h o to g ra p h s was ta k e n u s i n g Cu K a r a d i a t i o n ( \ = 1.541 8 ) t o
d e te r m in e t h e u n i t c e l l and t h e o r i e n t a t i o n o f t h e c r y s t a l .
Once t h e o r i e n t a t i o n was e s t a b l i s h e d , th e c r y s t a l was
t r a n s f e r e d t o a n E n r a f N o n ius PAD-3 f o u r c i r c l e d i f f r a c t o m e t e r
i n p r e p a r a tio n fo r d ata c o ll e c ti o n .
The c r y s t a l was c a r e f u l l y
a l i g n e d ( s e e C h a p te r I , E x p e r im e n ta l P r o c e d u r e ) and t h e 6-20
s c a n t e c h n i q u e was employed i n t h e d a t a c o l l e c t i o n . * ’ The
r e f l e c t i o n i n t e n s i t i e s w ere c o l l e c t e d i n two s e t s ; one o f
t h e t a from 4 . 5 t o 2 0 .0 ° and th e o t h e r from 2 0 .0 t o 25.0*^.
I n t h e f i r s t s e t , some o f th e r e f l e c t i o n s r e q u i r e d a n a t t e n u a t o r
c h e c k ( s e e C h a p te r I I , E x p e r im e n ta l P r o c e d u r e ) w h i l e i n th e
second s e t , t h e r e f l e c t i o n s were l e s s i n t e n s e a n d , t o save tim e
i n d a t a c o l l e c t i o n , no a t t e n u a t o r c h e c k s w ere made.
In th is
m an ner, 1418 i n t e n s i t i e s w ere c o l l e c t e d and i n t r o d u c e d i n t o
7
program DTFDAT, w hich c a l c u l a t e d t h e o b s e rv e d s t r u c t u r e
a m p l i t u d e s and t h e r e s p e c t i v e sigm as f o r t h e r e f l e c t i o n s .
T h is
i n f o r m a t i o n was punched on com puter c a r d s t o be used l a t e r i n
t h e s o l u t i o n and r e f i n e m e n t o f t h e s t r u c t u r e .
Between e ac h s e t o f 97 r e f l e c t i o n s c o l l e c t e d , t h r e e
s t a n d a r d r e f l e c t i o n s w ere m easured t o m o n ito r any s y s t e m a t i c
o r random f l u c t u a t i o n s i n t h e I n t e n s i t y d a t a .
The l a r g e s t change
i n t h e r e c o r d e d i n t e n s i t i e s was 0 . 1 % and t h i s s u g g e s te d t h a t no
s i g n i f i c a n t change o c c u r r e d i n t h e i n t e n s i t y d a t a .
SOLUTION OF THE STRUCTURE
The a p p r o a c h used I n t h e i n i t i a l d e t e r m i n a t i o n o f t h e
m o l e c u l a r s t r u c t u r e s i n C h a p te rs I and I I i s n o t a p p l i c a b l e t o
o rg a n ic s tr u c tu r e s .
In th e s o l u t i o n o f th e f i r s t two s t r u c t u r e s ,
t h e P a t t e r s o n i n t e r a t o m i c v e c t o r method was in v o k e d w h i l e h e r e
th e a p p l i c a t i o n o f d i r e c t m ethods i s more a p p r o p r i a t e .
To a p ­
p r e c i a t e th e d i f f e r e n c e betw een t h e two m e th o d s, some u n d e r s t a n d i n g
of th e s tr u c tu r e f a c to r is n ecessary .
The g e n e r a l form o f t h e s t r u c t u r e f a c t o r ,
can
view ed a s t h e r e s u l t a n t o f waves s c a t t e r e d by t h e atom s i n a
u n i t c e l l i n th e d i r e c t i o n hkJfc.
T h i s r e s u l t a n t can be r e p r e s e n t e d
i n t h e s i m p l e s t form as
where
| F | is
I' I•*“.
t h e a m p litu d e and 0 £ i s t h e p h a se a n g le w i t h r e s p e c t
to a s e le c te d o r ig i n .
I n g e n e r a l , when th e u n i t c e l l c o n t a i n s j
a to m s, t h e e x p r e s s i o n becomes
Fhk* From
p h a se a n g l e s
£j c i “ J-
t h e Laue e q u a t i o n s , i t i s p o s s i b l e t o f o r m u l a t e t h e
i n te rm s o f th e s c a t t e r i n g v e c t o r hkX and th e
i n d i v i d u a l a to m ic p o s i t i o n s x ^ , y ^ , z ^ , such t h a t
■p
_ v
* h k JL ~
f
2 n i ( h x , + k y , + jtz .)
e
3
3
3 •
147
S in ce f j i s p r o p o r t i o n a l t o t h e number o f e l e c t r o n s i n
atom j ,
I t can b e I n f e r r e d from t h e p r e c e e d i n g e q u a t i o n t h a t t h e
h e a v y atom w i l l be t h e l a r g e s t c o n t r i b u t o r t o th e ph ase and
a m p litu d e i n t h e c a l c u l a t i o n o f
T h e r e f o r e , once t h e h eav y
atom i s l o c a t e d , a c rud e e s t i m a t e o f b o t h t h e a m p litu d e and t h e
p h a se o f
i s o b ta in e d and by a s e r i e s o f d i f f e r e n c e maps
^ o b s ' ^ c a l c ^ * a d d i t i o n a l a to m ic p o s i t i o n s o f th e l i g h t e r atoms
can be fo u n d .
For o r g a n i c compounds d e v o id o f h eav y atom s, t h i s
a p p r o a c h would n o t be as v a l i d s i n c e a l l t h e atoms i n th e u n i t
c e l l p o s s e s s a p p r o x im a te ly t h e same a to m ic s c a t t e r i n g power
and c o n t r i b u t e t o t h e p h ase a n g le e q u a l l y .
The d i r e c t methods
a p p r o a c h does n o t in v o lv e l o c a t i n g a to m ic s i t e s , b u t , r a t h e r ,
makes d i r e c t a p p ro x im a tio n s o f t h e phase a n g l e Q£ u s i n g s t a t i s t i c a l
a r g u m e n ts .
T h is method was u sed i n th e s o l u t i o n o f th e p r e s e n t
s t r u c t u r e f o r t h e n o n c e n tro s y m m e tric s p a c e grou p P2^2^2^.
In
t h i s s p a c e g ro u p , t h e p h a se s o f th e hkO, h 0 £ , and Okf r e f l e c t i o n s
a r e r e s t r i c t e d by symmetry t o t h e v a l u e s 0 /1 8 0 o r 90/270 d e g r e e s .
U sing t h i s f a c t , a n o r i g i n can be d e f i n e d by c h o o sin g t h r e e o f
t h e s e p h a se r e s t r i c t e d r e f l e c t i o n s and a r b i t r a r i l y a s s i g n i n g t o
each a phase.
C e r t a i n r e s t r i c t i o n s a r e p l a c e d on t h e s e l e c t i o n
o f t h e s e o r i g i n d e f i n i n g r e f l e c t i o n s and t h e c r i t e r i a f o r t h i s
se le c tio n are:
(1)
No r e f l e c t i o n o f 2 n, 2n, 2n v a l u e can be u s e d ;
(2 )
No two r e f l e c t i o n s can be o f t h e same p a r i t y group
( I . e . , 203 (g g u ) and 043 (g g u ) i s f o r b i d d e n ) ;
(3)
The sum o f a l l t h r e e i n d i c e s may n o t be e v e n ( i . e . ,
S h a 2n, and U k = 2n, and 2 Z = 2n i s f o r b i d d e n ) .
In a d d itio n to
th e o r i g i n - d e f i n i n g r e f l e c t i o n s , two a d d i t i o n a l
r e f l e c t i o n s , one o f w hich i s u sed i n t h e d e f i n i t i o n o f t h e e n a n t i o m orph, a r e c h o se n from t h e g e n e r a l r e f l e c t i o n d a t a .
T hese r e ­
f l e c t i o n s have no r e s t r i c t i o n s on th e v a l u e s o f t h e i r p h a s e s .
T hu s, t h e v a l u e s o f 45, 1 3 5 , 225, and 315° a r e s y s t e m a t i c a l l y
perm uted f o r t h e s e two r e f l e c t i o n s f o r a t o t a l o f e i g h t com bln a tio n s.
By u s e o f th e S a y e r r e l a t i o n s h i p and sy m bo lic a d d i t i o n ,
t h e most p r o b a b l e p h a se s f o r t h e re m a in in g s t r u c t u r e f a c t o r s a r e
c a l c u l a t e d and a f i g u r e o f m e r i t (FCM), w h ic h i s r e l a t e d t o th e
p r o b a b i l i t y t h a t th e phaBes a r e c o r r e c t , i s d e te r m in e d f o r e ach
of th e e ig h t s e t s .
U t i l i z i n g t h e p h ases t h a t p ro du ce t h e h i g h e s t
FOM, a F o u r i e r s y n t h e s i s (E map) i s c a l c u l a t e d and th e p e a k s
d i s p l a y e d on t h e map a r e c a r e f u l l y p l o t t e d t o s e a r c h f o r a n image
o f t h e m o le c u le .
T h is i s t h e g e n e r a l p r o c e d u r e
t h a t was used
i n l o c a t i n g t h e c a rb o n and oxygen atoms i n t h e i n i t i a l s o l u t i o n
o f th e s t r u c t u r e .
O bserv ed s t r u c t u r e f a c t o r s f o r 1418 in d e p e n d e n t r e g
f l e c t i o n s , w ere i n p u t t o EGALC.
n o rm a liz e d s t r u c t u r e f a c t o r s E ..
T h is p ro g ra m c a l c u l a t e s th e
f o r e a c h r e f l e c t i o n by
12
- 2 B ( s i n 2 0/X2)
-2
J
J
w here
F , . . = observed s t r u c t u r e f a c t o r
hkjfc
Uhkjj = u n i t a r y s t r u c t u r e f a c t o r
^ikX ” wel-8^t:,-n 8 f a c t o r ( s p a c e g ro u p d e p e n d e n t)
B
= o v e r a l l te m p e r a t u r e f a c t o r
fj
= a to m ic s c a t t e r i n g f a c t o r
N
= t o t a l number o f r e f l e c t i o n s .
The 200 l a r g e s t n o rm a liz e d s t r u c t u r e f a c t o r s ra n g e d fro m 1 . 4 t o
9
3 . 4 and were i n p u t t o MULTAN, a program w h ic h may a u t o m a t i c a l l y
s e l e c t t h r e e o r i g i n d e f i n i n g r e f l e c t i o n s , a n e n a n tio m o rp h d e f i n i n g
r e f l e c t i o n , and one a d d i t i o n a l g e n e r a l r e f l e c t i o n .
The FCM f o r
t h e r e s u l t i n g e i g h t s e t s ra n g e d from 0 .6 1 t o 1 .1 5 .
E maps-were
c a l c u l a t e d f o r t h e two b e s t s e t s o f p h a s e s , b u t no image o r
p a r t i a l image o f t h e m o le c u le co uld be l o c a t e d .
The number o f E v a l u e s i n p u t i n MULTAN was d e c r e a s e d
and s t i l l no image co u ld be found.
The o r i g i n d e f i n i n g r e f l e c t i o n s
w ere s e l e c t e d m a n u a lly and even t h i s d id n o t p ro d u c e a n image o f
t h e m o le c u le .
In a l l ,
s e v e r a l v a r i a t i o n s o f i n p u t and d e f i n e d
o r i g i n s were t r i e d b u t no s o l u t i o n from p rogram MULTAN r e s u l t e d .
No r e a s o n f o r t h e d i f f i c u l t y i n l o c a t i n g t h e atom s c o u ld be
d e te r m in e d .
T h e r e f o r e , a second s e t o f program s c o n t a i n e d i n X -ra y
7 2 ^ w ere a p p l i e d t o th e p ro blem .
T h is s e t o f packaged program s
f o r c r y s t a l l o g r a p h i c p ro b le m s, c o n t a i n s a d i r e c t m ethods l i n k .
The s t r u c t u r e f a c t o r s were n o rm a liz e d i n s u b r o u t i n e NORMSF by
IF
hki I
|Eh k J =
—
*
“
U Sj f* >%
w here
*hkj& " s t r u c t u r e f a c t o r f o r r e f l e c t i o n hkj&
e
= w e i g h t i n g f a c t o r ( s p a c e g ro u p d e p e n d e n t)
fj
= a to m ic s c a t t e r i n g f a c t o r f o r jf*1
DK
2
= s c a l e f a c t o r t o e n s u r e <E > = 1 . 0 .
atom
O r i g i n d e f i n i n g r e f l e c t i o n s (0 7 1 5 , Q£ = 9 0 ° ; 1 0 3 , a = 9 0 ° ;
1 6 0 , Oi = 90°) and a n e n a n tio m o rp h d e f i n i n g r e f l e c t i o n ( 4 2 9,
0( = 4 5 ° ) , were m a n u a lly s e l e c t e d from a l i s t i n g o f r e f l e c t i o n s
w ith th e h ig h e st E v a lu e s .
In an F0M o f 0 .0 9 5 .
T h is s e l e c t i o n o f p h a s e s r e s u l t e d
The v a l u e o f FCM e x p e c te d f o r an i n d i c a t i o n
o f a p r o b a b ly s o l u t i o n should f a l l i n t h e ra n g e o f 0 . 9 5 t o 1 .2 0 .
S in c e t h i s v a lu e was f a r from t h e e x p e c te d r a n g e , two a d d i t i o n a l
r e f l e c t i o n s , 1 0 8 and 0 1 4 , whose p h a s e s a r e r e s t r i c t e d t o
0 /1 8 0 and 90/270 d e g r e e s r e s p e c t i v e l y , were used t o s u p p ly a d ­
d itio n a l a r b itr a r y phases.
The v a l u e s 0 ° and 90° f o r t h e two
r e s p e c t i v e r e f l e c t i o n s r e s u l t e d i n a n FCM o f 0 .6 6 .
Using th e
p h a s e s g e n e r a te d i n t h i s s e t , a n E map was c a l c u l a t e d and t h i r ­
t e e n s u s p e c te d a to m ic s i t e s w ere e x t r a c t e d .
A d i a g o n a l l e a a t - s q u a r e s f i t was a p p l i e d t o t h e s e
p o s i t i o n a l p a ra m ete rs r e s u l t i n g in R = 0 .4 9 .
At t h i s tim e t h e
l a r g e v a lu e f o r th e r e s i d u a l f a c t o r was i n t e r p r e t e d a s i n d i c a t i n g
an in c o r r e c t s t r u c t u r e .
However, C. T. G r a i n g e r , h a s r e p o r t e d
t h e r e s u l t s o f a d i r e c t m ethods s tu d y o f (3 -D -rib o p y ra n o sid e
(C&
in
t 'ie i n i t i a l l y c a l c u l a t e d R v a l u e was
0 .4 3 ev en a f t e r l o c a t i o n o f a l l e l e v e n o f t h e c a rb o n and oxygen
atom s i n t h e m o le c u le .
W ith t h i s i n m ind , a F o u r i e r d i f f e r e n c e map was c a l ­
c u l a t e d u s in g 933 o b serv ed r e f l e c t i o n s ( I ( n e t ) > 1 . 0 a ( I ) ) and
tw e lv e o f th e t h i r t e e n p e a k s p r e v i o u s l y f i t b y d i a g n o a l l e a s t squares.
F o u r a d d i t i o n a l n o n -h y d ro g e n atom s w ere l o c a t e d i n t h i s
map and a f t e r t h r e e c y c l e s o f r e f i n e m e n t a n R v a l u e o f 0 .4 1
re su lte d .
The two r e m a in in g n o n -h y d ro g e n atoms w ere l o c a t e d on
a n a d d i t i o n a l d i f f e r e n c e map and b lo c k d i a g n o a l l e a s t - s q u a r e s
was perform ed f o r t h r e e c y c l e s w i t h a w e i g h t i n g scheme o f
w = l / ( s i g F q)
and
= 0 .2 1 .
2
a p p l i e d t o e a c h r e f l e c t i o n , y i e l d i n g R = 0 .3 2
T hree a d d i t i o n a l c y c l e s v a r y i n g t h e i s o t r o p i c
t h e r m a l p a r a m e te r s on t h e c a r b o n and oxygen atoms w e re c a r r i e d
o u t g i v i n g R = 0 .2 7 7 and Rw = 0 .1 5 1 .
To t h i s p o i n t t h e oxygen atom o f t h e OH g ro u p had b e e n
h e l d c o n s t a n t In o r d e r t o d e f i n e t h e o r i g i n o f th e c e l l .
S in c e
t h i s atom a p p e a re d t o e x h i b i t h i g h th e r m a l m o tio n , atom C3 was
f i x e d a s a new o r i g i n d e f i n i n g p o s i t i o n and t h r e e a d d i t i o n a l
c y c l e s o f f u l l m a t r i x l e a s t - s q u a r e s w ere c a l c u l a t e d w i t h 733 r e ­
f l e c t i o n s ( X ( n e t) > 2 . 0 cr ( I ) ) p ro d u c in g R = 0 .2 3 7 and
= 0 .0 9 1 .
Twenty h y d ro g e n atoms w ere l o c a t e d from a F o u r i e r d i f f e r e n c e map
and a f t e r s e v e r a l c y c l e s o f r e f i n e m e n t o f t h e c a rb o n and oxygen
a to m ic p o s i t i o n s and r e - l o c a t i n g t h e c e n t e r s o f t h e H atoms i n
d i f f e r e n c e maps, th e a g re em e n t f a c t o r s d ro p p e d t o R = 0 .1 6 4 and
R = 0 .0 6 0 .
W
At t h i s p o i n t a n i s o t r o p i c th e r m a l m o tio n was i n t r o d u c e d
f o r th e t h r e e oxygen atom s and w i t h atom C4 h e l d c o n s t a n t , t h r e e
c y c l e s o f w e ig h te d f u l l m a t r i x l e a s t - s q u a r e s gave r e s i d u a l v a l u e s
o f R k 0 .1 1 7 and R^ = 0 .0 4 2 .
Three a d d i t i o n a l c y c l e s , v a r y i n g
o n ly t h e p o s i t i o n s o f t h e h y d ro g e n atoms p ro d u c e d R = 0 .1 1 4 and
Rw = 0 .0 4 0 .
The a p p ro x im a te p o s i t i o n s o f t h e s e h y d ro g e n atoms
a r e by no means t o be c o n s t r u e d a s c o m p le te ly r e l i a b l e s in c e
th e r e l a t i v e c o n tr ib u tio n to th e r e f le c te d i n t e n s i t i t e s of th e se
h y d ro g e n atom s i s s m a l l .
F i g u r e 10 i s a s t e r e o v ie w o f t h e com­
p l e t e d s t r u c t u r e w hich i n c l u d e s t h e s e a p p ro x im a te h yd rog en
lo c a tio n s.
T a b le X I I I c o n t a i n s t h e p o s i t i o n a l p a r a m e te r s f o r a l l
t h e atoms i n th e a sy m m e tric u n i t .
The o b s e r v e d and c a l c u l a t e d
s t r u c t u r e f a c t o r s a r e found i n T a b le XIV.
Bond l e n g t h s and a n g l e s
f o r t h e m o le c u le a r e i n T a b le XV, and t o r s i o n a n g l e s a r e l i s t e d i n
T a b le XVI.
TABLE X III.
Atomic C o o r d in a te s And Thermal P a r a m e te r s F o r
T a m a u lip in -A ,
TABLE X II I .
Atom C oord in ates fo r th e [ ^ 5^ 20 ^ 3 ^ M o lecu le.
Atom
x (10
4
ct)
y ( l o 4 a)
z (104 <?)
B (10 a)
Cl
- 0 .3 0 1 4 (17 )
- 0 .3 8 3 9 ( U )
- 0 .8 0 9 9
(7)
4 .4
(3 )
C2
- 0 .1 6 6 6 (18 )
- 0 .4 7 7 7 (13)
- 0 .8 1 4 2
(8 )
5 .6
(3 )
C3
- 0 .0 4 8 9 (17 )
- 0 . 4 4 8 6 (11)
- 0 .8 9 8 8
(6 )
4 .2
(3 )
-0 .3 3 3 6
- 0 .8 9 6 8
3 .0
(2 )
C4
0 .0 1 8 3
C5
- 0 .0 7 6 4 (13)
- 0 . 2 4 9 9 (1 0)
-0 .9 3 4 0
(7 )
3 .3
(2)
C6
- 0 .0 5 9 9 (18)
-0 .1 3 0 7 (11)
- 0 .9 0 8 2
(8)
3 .7
(3 )
C7
- 0 .2 4 4 2 (16)
-.0.0783 (12)
-0 .8 9 1 2
(7)
4 .4
(3 )
C8
- 0 . 3 1 4 8 (20)
- 0 . 0 8 8 4 (18)
- 0 .7 9 5 6
(8 )
5 .2
(4)
C9
- 0 .4 0 4 9 (1 6 )
- 0 .2 0 0 3 (10)
-0 .7 7 2 2
(7 )
4 .6
(3 )
CIO
- 0 .2 8 8 6 (15)
- 0 .2 9 4 0 (11)
-0 .7 5 2 7
(8)
4 .3
(3 )
C ll
-0 .2 1 2 7 (1 8)
0 .0 3 6 3 (12)
- 0 .9 2 8 8
(8 )
4 .9
(3 )
C12
- 0 .0 6 9 5 (2 4)
0 .0 3 4 1 (18)
-0 .9 8 8 1
(9 )
5 .2
(3 )
C13
- 0 .3 0 5 0 (2 1)
0 .1 2 7 4 (13 )
- 0 .9 1 0 5
(9 )
7 .5
(4)
C14
- 0 .1 7 1 8 (1 9 )
- 0 .2 7 4 9 (13)
-0 .6 7 4 3
(9 )
7 .6
(4 )
Cl 5
0 .1 7 4 5 (1 6)
- 0 .3 2 3 2 (10 )
-0 .8 3 7 1
(7 )
4 .7
(3 )
01
- 0 .2 3 5 1 (12 )
- 0 .5 8 4 0 (11)
- 0 .8 2 3 3
(6)
*
02
0 .0 1 2 6 (16 )
- 0 .9 8 3 6
(5 )
*
03
- 0 .0 0 8 0 (1 4)
- 0 .0 6 5 9 (11)
0 .1 0 3 1 (1 0 )
- 0 .0 4 1 1
(5 )
*
HI
- 0 .1 0 1 6 (131)
- 0 .4 8 9 8 (85)
- 0 . 7 5 2 3 (5 3 )
5 .0
H2
- 0 .1 4 3 5 (159)
- 0 .4 5 8 1 (87 )
- 0 .9 5 4 2 (5 7)
5 .0
H3
0 .0 3 4 5 (126)
- 0 . 5 1 3 8 (85)
- 0 .9 1 8 2 (62 )
5 .0
H4
- 0 .1 8 5 0 (114)
- 0 .2 9 3 1 (92)
- 0 .9 7 7 1 (5 4)
5 .0
H5
0 .0 0 8 4 (127)
- 0 . 1 4 5 0 (98)
- 0 .8 4 9 9 (6 7 )
5 .0
H6
- 0 .3 0 8 0 (12 4 )
- 0 .0 9 8 9 (105)
- 0 .9 4 1 8 (59 )
5 .0
155
TABLE X III.
(C ontinued)
Atom
x (1 0 4 <*)
y ( 104
0)
z (1 0 4
B (10 a)
H7
- 0 .2 0 6 9 (148)
- 0 .0 9 1 2 (94 )
- 0 .7 4 6 0 (64)
5 .0
H8
- 0 .3 7 1 2 (154)
- 0 .0 2 2 7 (95 )
- 0 .7 8 7 5 (5 5)
5 .0
H9
- 0 .4 7 4 0 (114)
- 0 .2 3 9 3 (100)
- 0 . 8 2 7 8 (60)
5 .0
H10
- 0 .4 9 0 6 (130)
- 0 .1 8 1 0 (90)
- 0 .7 0 8 8 (60)
5 .0
H ll
- 0 . 3 9 4 6 (146)
- 0 .3 7 1 5 (95)
- 0 .8 7 1 7 (6 6)
5 .0
H12
- 0 . 2 6 6 5 (137)
- 0 . 2 6 0 5 (107)
- 0 .6 2 4 6 (65)
5 .0
H13
- 0 . 1 3 2 3 (166)
- 0 .3 4 3 0 (107)
- 0 .6 5 3 8 (65 )
5 .0
H14
- 0 .1 0 4 0 (133)
-0 .2 0 0 1 (82 )
- 0 .6 8 9 0 (6 9)
5 .0
HI 5
0 .2 9 7 5 (134)
- 0 . 3 5 5 6 (108)
- 0 .8 6 4 6 (64)
5 .0
HI 6
0 .1 6 2 8 (143)
- 0 .2 5 8 7 (113)
-0 .8 438 (65 )
5 .0
HI 7
0 .1 3 6 0 (122)
- 0 .3 3 5 2 (90 )
-0 .7 6 6 7 (6 4 )
5 .0
H18
- 0 . 2 3 4 4 (129)
0 .1 8 5 0 (91 )
-0 .9 3 2 5 (54)
5 .0
HI 9
- 0 .3 9 2 8 (152)
0 .1 1 7 9 (94)
-0 .8 6 0 1 (65)
5 .0
H20
- 0 .2 3 2 7 (133)
- 0 .6 2 2 8 (94)
- 0 .8 8 7 5 (55)
5 .0
* A n i s t r o p i c t h e r m a l p a r a m e te r s f o r oxygen atom s a r e o f t h e form
exp < - ( h 2p11 + k 2 0 2 2 + * ^ 3 3 + 2 ^h kP i 2 + ^ 1 3
Atom
104 pix
104 p22
104 P33
104 p12
+ kjep23 > ) ) .
104 p13
104 p23
01
364 (2 8)
66 (8)
114 (6 )
-6 9 (12) 47 (1 3 )
12 (7)
02
292 (2 5 )
69 (8 )
69 (5 )
10 (12) 25 (11)
12 (6)
03
507 (3 6 )
85 (9 )
78 ( 6 )
- 6 (16) - 6 (12)
19 (7)
TABLE XIV.
The O bserved And C a l c u l a t e d S t r u c t u r e F a c t o r s
F o r T a m a u lip in -A ,
- r i ’iT iiiiii’iiT ii'irrT in ri:* ? ::?
■777 7 71 77 7 1 7 1 1 1 7 7 1 * * * 7 7 7 7 7 7 7 7 7 7 * 7 7
7 l a £ * s l ! J <" I I : ! S ! ! ; s : *S S ! I I 5 * * i i " * I * i * * ; 7 t i S J » S s S s S I 7 I S 3 S r s t s S " J J S S J 3 ; s 7 i s : i s j * ; ; " j j j * ; s j j ; r ; i s s j C r s ; j
J 77* 77 7 7 7 ' ' 7 7 7 T T 7 " 7 7 T 777 7 7 7 7 7 7 7 * 7 7 7 7 f 7 T 7 7 T T 7 T 7 2 2 * 7 f T 7 f 7 7* 77 t T f * 7 7 f f t 7 7 7 7 r T 7 7 T f 7 T 7 T 7 7 7 7 7 7 f 7 T * 7 7 ! 7 T 2 * 7 T 7
‘ 7 7 7 7 1 7 7 7 7 1 7 1 7 1 7 7 7 7 7 : ? 7 S 2 ; - - ' * 7 7 7 7 7 r 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 1 7 7 7 7 7 77 H i l l 7 1 7 1 7 1 7 7 7 1 : 1 7 1 7 7 * * * * 7 7 7 1 7 7 7 7 1 7 7 7 7 7 7 7
■ 7 r7 7 t:* 777r777f:''777T :7rs:*777T 7:7777777*77777f7:i*777tr;7 j:7 7 ;7 7 T ::S 7 7 7 7 T 7 7 7 ::7 7 7 T rf7 7 ::-7 7 7 1 7 7 7 r:7
............. ........................................7 7 T 7 7 T T 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 f 7 7 7 7 7 7 7 f 7 7 7 7 7 7 7 7 7 7 7
■•7 7 7 7 2 7 7 7 7 7 7 7 7 * 7 7 7 7 7 7 7 7 2 ; * 7 7 T 7 T 7 7 T
7*7T::77*t777T77:;*771
7 7 7 77 J * - 7 7 7 7 7 1 7 * 7 7 7 7 7 7 7 7 7 1 t = ’ 7 7 7 7 7 7 T S : 2 5 S T 7 7 t
■ 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 : 2 : ! 2 2 2 j ; : * " * " * ' ' “ * i 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 T 7 T 7 7 7 7 7 77777 7 7777 7 777777 77777
j S S S s s i i t s j s i t s s e s ^ s s i s t s s j j j E - s s j j s j ^ r s s j i i j t t s t j s j j s j i i j j u s s j j s s j t s r i i i s j i s i s s r c i S s a s i s j s j j j j ! *
• 1 7 2 2 2 1 7 1 1 1 7 : * 7 T 7 1 1 i : " 7 7 7 7 i : * 7 t 7 7 7 7 7 7 1 2 2 2 " 7 7 7 1 7 1 7 7 2 2 2 * 1 7 7 1 1 1 1 ? 2 2 : : * 7 T T f 1 S 2 2 2 * : 7 i : i 1 7 2 * T 7 7 T 1 1 7 1 2 * 7 7 717
• 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 : : : : : : : ; : : : : .............. • • • r f T 7 T 7 7 7 T T 7 7 7 7 7 7 7 7 7 7 7 7 T 7 7 7 T 7 7 7 7 7 7 7 7 7 7 7 7 7 1 1 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7
* 2 7 7 7 7 7 7 2 t T 7 * 1 7 7 7 7 7 7 1 * : ; ; * 7 7 7 7 7 7 7 7 : 2 2 7 7 * 7 7 7 T : * * 2 ; * : t 77 7 7 * 7 2 2 2 2 * 7 7 7 7 1 7 7 * * 7 7 7 7 7 7 1 7 S 2 ; * 7 T 7 7 7 : 7 7 : 2 5 * t 7 7 ? 1
■ * 2 2 2 2 2 2 2 2 2 2 2 2 * * * * * ........... * T 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 W 7 7 1 7 f T 1 1 7 1 7 1 7 1 7 7 7 7 7 7 1 1 1 7 7 7 7 1 1 7 7 7 1 7 7 7
j
:
:
:
a
s
:
:
s
:
3
S
!
S
s
s
:
r
7
:
s
*
:
i
;
i
:
s
:
s
5
=! *; *•
■ T T T 1 ? 7 :2 2 7 7 ? 7 :2 ::7 7 7 7 1 7 7 ::s:* 7 7 7 7 7 7 7 :7 ::::2 :* r 7 7 :r i7 1 T := * T 7 ? 1 T :i* 7 :7 7 7 7 :2 * 7 T 7 1 7 :7 :: * 7 T 7 7 7 7 7:2*T77717
................ 7 7 7 7 7 7 1 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 : 7 7 7 7 7 7 7 7 7 7 1 7 7 7 t : 7 : 7 : T : ? : r f : : : : : T 1 7 7 7 7 7 7 7 1 7 7 7 7 7 7 7 7 7 7 7 f 7 7 7 7 7 7 7
-i::2 ::ss!is:i2 2 sss::!2 :::i:s2 * :st;5 « » s* s:2 is* ::ti:::s::2 i;;j::;# jt:jt:i* j:5 ::si|:|2 je ;:s:rsi;;::jsjj
J T1 1222 7 7 7 1 7 : : : 7 7 7 7 1 7 : 2 : : T 7 T 7 7 7 : : 2 * 7 7 7 7 7 * : 2 2 2 ; 7 7 7 : 1 7 * 7 7 7 7 1 7 7 7 2 2 7 7 f t 7 7 2 2 2 * 7 7 7 7 7 : 7 7 1 1 7 7 7 7 7 1 7 : i 7 7 7 ? t 7 * 7 7
................ 7 7 7 7 : 7 7 7 7 : : 7 : : 7 7 7 7 Y 7 7 7 7 7 1 7 7 7 7 7 7 7 7 7 7 ? ? 7 1 7 7 7 T 7 7 f 7 t : i 7 7 7 7 1 7 1 7 1 7 7 : : 7 : : i i 7 T 7 7 7 7 7 7 7 : : : 2 : : : : i 2 2 2 ^ 2 : : *
TABLE XV.
Bond L engths And A n g les Found For Taraaulipin-A,
159
TABLE XV.
Bond L e n g th s (A n g stro m ^ And Bond A n gles (D e g re e s ) For
^C15H20°3^'
Bond
(10^ <j)
Bond
(10^ cr)
Cl - C2
1 .5 5
(2 )
C8 - H7
Cl - CIO
1.37
(2 )
C8
-
H8
1 .1 2 (11 )
0 .9 1 (12)
Cl - H ll
1.17 (1 0)
C9
-
CIO
1 .4 8
C2 - C3
1 .5 8
(2 )
C9
-
H9
1 .0 8 (10)
C2 - 01
1J39
(2 )
C9
-
H10
1.17 (10)
C2 - HI
C3 » C4
1 .0 5
(9 )
CIO
-
C14
1 .4 9
(2)
1 .4 8
(1 )
C ll
-
C12
1 .4 2
(2)
C3 - H2
1.1 1 (10)
C ll
C13
1 .3 4
(2 )
C3 - H3
1 .0 6 (1 0 )
C12
-
02
1 .3 6
(2 )
C4 - C5
1 .3 6
(1 )
C12
-
03
1 .2 3
(2)
C4 - Cl 5
1 .5 2
(1 )
C13
-
HIS
0 .9 4 (10)
C5 - C6
1 .4 8
(2 )
C13
-
H19
1 .0 2 (11)
C5 - H4
1 .1 8
(9 )
C14
-
H12
1 .0 6 (10)
C6 - C7
1 .6 0
(2 )
C14
-
H13
0 .9 2 (13)
C6 - 02
1 .4 6
(2 )
C14
-
HI 4
1 .0 6 (1 0)
C6 - H5
1 .0 2 (1 0 )
C15
-
HI 5
C7 - C8
1 .5 1
(2 )
C15
HI 6
1 .1 2 (11)
0 .7 8 (14)
C7 - C ll
C7 - H6
C8 m C9
1 .5 0
(2 )
Cl 5
-
H17
1 .0 9 (10)
0 .9 3
(9 )
01
-
H20
1 .0 5
1 .5 5
(2 )
(2)
(9)
160
TABLE XV.
(C o n tin u e d )
Angle
C2-C1-C10
(1 0 a)
Angle
( 1 0 a)
C8-C7-C11
1 1 8 .3 (1 3)
C1-C2-C3
1 22 .9 ( 1 1 )
1 0 6.0 ( 1 0 )
C7-C8-C9
1 1 6 .2 (13)
C1-C2-01
1 1 3 .6 (ID
C8-C9-C10
1 1 4 .4 (11)
C3-C2-01
110.7 ( 1 0 )
C9-C10-C1
1 1 5 .6 (10)
C2-C3-C4
1 1 3 .5
(9 )
C9-C10-C14
1 1 4 .7 (11)
C3-C4-C5
118.7
(7)
C1-C10-C14
1 2 9 .7 (12)
C3-C4-C15
1 1 2 .3
( 6)
C7-C11-C12
1 0 9 .8 (14)
C5-C4-C15
1 28 .1
( 6)
C7-C11-C13
1 2 5 .5 (13)
C4-C5-C6
1 2 3 .8
(9 )
C12-C11-C13
124.6
C5-C6-C7
10 9.6 ( U )
C11-C12-02
1 1 1 .4 (15)
C5-C6-02
1 1 0 .5 ( 1 0 )
C11-C12-03
1 3 3 .1 (19)
C7-C6-02
1 0 5 .4 ( 1 0 )
02-C 12-03
1 1 5 .5 (1 5)
C6-C7-C8
1 1 6 .6 ( 1 1 )
C6-C7-C11
9 8 .6 ( 1 0 )
C12-02-C6
(15)
1 0 8 .3 (11 )
TABLE XVI.
T o rsio n A ngles Found For T am aulipin-A ,
A
a
c
C I
C I
c t
C 1
e %
C 1
C 1
C |
C 1
c t
C T
c ■
C fi
C f
C f
c t
C I
c a
c a
C 3
C 3
c a
C )
C 3
C ft
c ft
e a
c a
e a
c a
cm
e ta
Gl6
e ta
ci a
CIO
C K
C t
C3
c a
C J
C J
c t
c a
c »
C 4
C •
C 4
G 4
C 4
c a
C fi
e a
C fi
c •
e e
c a
Ct*
c ia
c ia
c t*
C4
C 4
6 4
C 4
C4
C 4
C 4
C4
C 1
c ■
C*7
C 7
C7
C 7
C 7
C 7
0
C 4
c a
c a
c a
c a
c a
c a
cu
C ll
C ll
C ll
C 7
C7
C
c
C fi
0 1
C a
c t
c a
Cl*
CI4
Cl*
CIO
CIO
c *
C 4
H fi
h fi
e i
C 1
C 1
C ft
C4
CIS
Clft
c ia
c a
c a
« a
M3
C4
c a
c a
Ml
Hia
Ml*
41 1
C fi
C 3
Clft
e ta
e ta
c 7
c t
e t
c a
C4
c a
c a
c a
C ll
C tl
C ll
c ifi
c a
o a
c a
c a
c a
M7
h a
Cl*
c ia
Cl 3
Hta
e a
c a
C A
C I
C4
C 4
C 4
C 4
C 4
c *
C 4
C fi
C9
C 9
c a
c fi
c a
c %
c a
c «
c a
c •
C4
e <
C4
C «
C4
c •
C 7
C 7
C7
G 7
C 7
C 7
C 1
C 7
C 7
C t
t 7
c a
c a
fi
• Ml
0
fifi
C4
4 fi
H fi
HtO
c a
n a
fflO
mix
Ml fi
HI#
c a
a#
c a
c ia
4 fi
H fi
CIO
Ml
Hie
C4
H 4
Mitt
Mft
HIT
0 1
M1
H fi
H fi
C 7
G fi
H ft
HU
Hta
Mr
Hta
H»
M fi
Mft
HI*
HIT
e a
cu
h a
C ll
Clft
c a
H 7
M•
C ||
CI3
M|«
C ll
H4
Cl*
CIO
M4
HIO
h a
M V
o a
Hta
>aa
ctfi
O
H
fift
■ til
-o e .s
• t o o .f t
a o .4
• t e a .*
• 7 .4
ita « i
• t t a .f i
•ia .%
130*0
t4 4 .fi
- 1 1 -ft
- 0 7 .f i
0 1 .7
•1 3 0 * 7
0 4 .1
-o o -t
4 4 .4
•ia .fi
ta a .fi
—
4 .4
40 .1
it * . a
-4 4 * 3
t7ft.fi
*ft**fi
tOfi.4
- 1 * 1 .0
-131*1
111.7
•1 0 .7
lOT.fi
- lf if t .0
1 03.4
-fift.fi
J tt.l
ita .fi
• I 3 t .f i
—1 7 * |
a * .*
a a .fi
•143*7
- t* « 0
1 4 0 .0
- 1 1 .7
- 4 3 .0
a a .a
t*fi«4
• 4 .4
•140*0
-tJO .fi
- a .i
• 4 .0
• 1*7
77*0
-4 7 * 1
• |««*ft
I0 4 .fi
- t 0**0
- a .a
10^9
11*0
• 4 4 ,7
- if it .a
- 9 3 .4
Aft
OC
CS
94
1*04 t .o a
1 .4 0
1 .0 0 Uftfi 1*14 1 .7 9
1.4 0 t*a» 0 .4 4
i.n
1,3ft 1 .1 4 3*03
1*37 1.44
1.3 7 1*40 t .1 9
1*37 1*44 1 .1 7
1 .3 7 1*44 1 .1 9
1 .3 7 t . 4 f O.fift
1*77 l*4fi 1*34 3 .4 3
1*00 1.37 1.4ft
t«ft9 1*37 t .« a
1*0* 1 .4 0 1*34
1 .1 * 1.44 1 « U 3* KB
■•Sfi l . l i
1*31 l . f i f
o*a« 1*91
i.n
l*Sfi 1.00 1*37
i . a a t.OB t * l»
i d ii i . i a
1*14
1*44 1.3a 1 .4 1
l*4ft 1.34 1*04 f i . U
1 .4 4 t .f t i 1*13
1 .4 1 l.ftfi 1*00
l .f t l 1 .00
t .« a
1.4 4 l - f t l 1 ,3 4
M l t*aa 1*04
1*44 t . i a
1*31
1*44 o .a a 1*31
1.3 4 t .4 4
1*44
1*34 t .f t l 1.4 7
1 ,3 4 1.44 t*03
I.O f t.fifi UTfi
l*9fi 1*40 i .7 a
l . f t l l .« 0 1*91 1.74
t»!V 1 .0 0 1*fi!
1.3 4 1 .4 1 1*19 1*49
1.3 4 t*«a a * ta
1*34 l .f t l i . i t J .M
t *34 i . t i
t* « e
1*34 t . a i l*CO
! * • • t*aa 1*41
1*44 1 .M
1*99
1*44 I *40 O.fifi
1 .4 4 1*47 1 .3 4
1*44 1 .3 4 1 * 9 |
1**0 l .f t l 1*09
1*40 t - a t 0*«« 1 .7 ft
1*44 1*41 1 .1 3 3 .9 1
t.ftO i .a a 1,4 1
l.ftQ i . a a 1 .3 4 3*44
1*40 l.ftO I.Tfi
1*47 1*34 1*41 1 .3 9
1 .4 0 1 *44 1.0 4
1*44 1*47 1 .3 4 1 .3 4
U l i * t e t.ftft 3 .3 0
1.4 1 1 .9 4 i . n
1*94
l - f t l t.ftft 1,1 7
l . f i l O.fifi 1 .4 1
1.3 1 1 .1 3 1*41
I .SO l . 4 f l- 3 « 1*44
I .SO 1 .3 4 o *ar
1*34 1 .0 4
141
l.ftO 1.7 1 ft.fiT
l* « t 1*40 1*47 3 .7 9
1.91 1*40 t .0 3 1 .9 4
A
c a
c a
c a
c a
c «
C fi
c a
c a
c a
C I
c a
c a
CIO
e tc
c to
ci e
CIO
e tc
C ll
C ll
C tl
C ll
C tl
C ll
C ll
C ll
C ll
C ll
CI3
CIS
Clft
Clft
e ta
Clfi
Clft
CIS
C19
Clft
0
c
0 1
0 1
0 1
0 1
H
H 1
H
N
H4
H •
h
m
a
a
H4
M7
H 7
h a
h a
H |»
Ml J
MIS
H19
HU
a
c
e
mi
C 7
C7
C 7
c a
e a
c •
c a
Cll
C ll
Clfi
e ta
1*7.0
MU
HIS
HI fi
- f t. 3
94*7
19ft *7
1 0 -0
- l i f t . ft
tia .fi
• 3 .4
41*4
149.1
•ft 9 .0
140*1
1 9 .9
-9 4 *1
-199*3
119*7
- 1 0 4 .7
0 1
-tft.f t
c •
CIO
CIO
CIO
CIO
C 1
C 1
c a
c a
Cl 4
Clft
C 7
C T
C 7
C T
HI ■
C ||
cu
C ll
C tl
a ■
C ll
cu
CIO
c ia
ci e
C 4
C4
C 4
H19
HIT
C 1
c
fi
C 1
C4
C 4
Ctfi
C 1
C fi
c a
C1
C 9
c e
C 7
C 7
C 7
c a
c a
c a
c a
H IJ
HU
C1B
C lft
Hta
Hta
H lft
H ta
C tl
a i
e io
c t*
cu
M«
C 7
C 7
h 7
m
Ma
H7
a
C 1
H I
c tft
H it
Clft
MIS
Mft
c t#
C fi
C 1
e a
C 9
HU
M il
C6
c a
C4
c a
CIS
C7
CIS
CIS
H19
C 4
C 7
Clfi
Ct
c a
c a
C3
C 9
C ft
Hta
Mia
c I
c a
C 3
a
M7
H0
H9
H7
M4
m i
K%
0 t
c a
e t
c a
e a
C tl
C4
c a
c a
C 4
Clft
HI4
c ts
H9
H9
C fi
411
M ft
MID
►1
►3
H ft
►t?
MIS
HU
H >
-
M3
H 4
H fi
Hlft
Ml |
►*
H3
HfiO
H1
M ft
H 7
4 ft
HI 1
H ft
Htft
H ft
H |«
Htft
C |4
Hta
H lft
HIT
Clft
H lft
HIT
H IT
414
Clft
CIS
a a -ft
•aa * o
ift.fi
143*3
• 7 7 .9
mo
e a
C 7
C ll
C 1
C 3
C 3
1
H |
• t« » * 4
ia i.f i
-•••i
iftfi.i
171*9
174*0
4 7 1 .t
•49* ft
•1* 4.4
- 7 1 . ft
-1 71 * 4
33*3
•13*3
- 9 3 ,4
4 3.3
- 3 4 .0
-fiO.ft
93*4
ll f t.f i
•177*7
140.0
ao*a
-1 9 0 .3
I3ft.fi
•147*0
IAI.fi
•110*7
131*1
- I T * .*
7 7 .9
7ft , 7
-fi3*ft
1 IC .0
-130*7
MI7
119*9
117.1
-111*9
-147*9
AS
1*91
1.11
1 «Bt
1.99
l«BB
1 .9 9
t.sm
1 .9 0
l.fift
1*40
t.ftft
I.4 B
1*17
1.37
l.fift
t.ftft
i«fta
1.4ft
1*90
1-0C
1.90
1*90
I.Tfi
t.fifi
1*41
1 .4 1
l*4fi
1*3*
t*3fi
1*34
1*49
K
1 .9 0
1.99
1*09
1 .4 9
1*01
1*91
4 .7 9
t «13
1.37
1*ftft
1*49
t *41
1*99
1 *90
1.00
1*99
l* IB
0 .9 0
1,9ft
t* ftl
1.04
1*91
0 ,0 7
1*94
1 .3 4
1,34
t.Tfi
1 .4 7
1*00
l.ftfi
1*37
l.fift
l.fift
i* * a
l.ftfi
t* fti
1*03
t.fifi
1*00
1.3ft
1*3*
1.79
1*47
1.47
1*34
1.04
1*04
1-04
1*04
1 .4 9
1 *4ft
1 ,4 0
l-ftfi
l->*
1.79
t.o a
l.BB
1-39
1.90
1.40
i.a a
t.fifi
l.BB
l.B *
1,0ft
1 ,3 9
1*40
1.40
1*03
o .a a
0.0ft
o -ao
o .a *
• .ft*
1*13
1.11
1.9ft
1.9ft
l-tfi
1 .90
1*00
a .99
1*09
I .U
0*0fi
1.IB
I.CO
t.fifi
t.r a
1,90
t.OB
1.7*
l*XJ
1.3ft
I . 73
!*»(
l.f tl
CO
DA
■*4«
3,71
3 ,0 0
3*«
3 .0 7
3*09
7-41
t.a a
i.a a
a .s a
V,70
3 .3 4
1*70
3-94
a .s a
1 .3 4
I.Tfi
1,4*
1*90
0,0ft
1.41
1*4!
1*10
l.ltt
0*ftt
1 ,3 4
1 .3 9
1 .04
a .* *
1.13
1 .9 0
I.SO
1 ,4 7
1,03
C.99
1 .1 3
1 .0 4
a.9ft
0*07
1 .9 4
ft. 07
1 -OS
9.0ft
1,3ft
1*30
1 .9 9
1 ,1 7
1.10
I .N
t.ftft
1*03
1 ,70
t* t o
1*10
0*04
1*04
ft- ft ft
1*71
1*37
1 ,19
0 .0 *
l.lft
l.« 3
o -at
«*««
1 .1 3
a .T i
1 .3 9
1*17
l.tl
1 .1 7
1*39
1*30
l.tl
l.tt
t. a o
i .a a
t.ftft
I.AA
3 . Sfi
1 .0 1
fi-flf
a .s e
a.FB
1*71
141
fi»aa
3*43
4 .1ft
3 ,3 9
1*49
3*01
3 .1 3
3 .0 7
3 .4 0
3*94
4 ,9 7
3 ,9 9
I tM
3 .4 7
1.00
1*44
3*09
• *40
fi.74
t.O ft
K.70
f i.tl
3*44
4 ,9 0
fi.Tft
■*97
4 . St
4*99
3 .0 0
4 .7 4
s .a n
3*04
4 .7 3
4*40
4*34
1,9*
1*04
1**0
1.71
1*99
1*94
WftJ
162
DISCUSSION
C l a s s i f i c a t i o n o f t h e s e s e s q u i t e r p e n e l a c t o n e s i s based
on t h e n a t u r e o f th e two d o u b le bonds i n t h e c y c l o d e c a - 1 , 5 - d i e n e
r i n g s y ste m , i . e . , w h e th e r t h e y a r e c i s o r t r a n s .
th u s , four d i s t i n c t c a te g o r ie s :
14
T h e re a r e ,
tra n s -tra n s . tra n s -c is. c is -tra n s .
and c i s - c i s f o r A^ and A ^ ^ * ^ r e s p e c t i v e l y .
The f i r s t t h r e e
c a t e g o r i e s c h a r a c t e r i z e t h e g e r m a c r o l i d e s , m e la m o p lid e s , and t h e
h e lia n g o lid e s,
14
and t h e p r e s e n t compound e x h i b i t s t h e t r a n s - t r a n s
c o n f ig u ra tio n o f th e g e rm a cro lid es.
The o v e r a l l c o n f i g u r a t i o n o f ta m a u lip in - A ( F i g u r e 10)
i s t h a t p r e d i c t e d by F i s c h e r e t a_l
2
and i s s i m i l a r t o t h e con-
f i g u r a t i o n found i n t h e X -ra y d i f f r a c t i o n s t u d y o f d o s t u n o l i d e .
4
The bond l e n g t h s and a n g l e s found i n t h i s s t r u c t u r e d e t e r m i n a t i o n
do n o t d i f f e r s i g n i f i c a n t l y from t h e v a l u e s r e p o r t e d f o r
m elam podin,
13 14
*
w h ic h i s a member o f th e m e la m o lld e s .
Both
s tr u c tu r e s co n tain a b ic y c lic b a sic u n it c o n sis tin g of a fiv e
atom l a c t o n e r i n g t r a n s fu s e d t o a t e n membered r i n g a t C6 and
C7.
I n ta m a u l i p i n - A , t h e two c a rb o n atoms bonded t o t h e t e n
membered r i n g a t atom s C4 and CIO a r e sy n t o one a n o t h e r and t h e
OH g ro u p bonded t o atom C2 i s s i t u a t e d a n t i t o t h e s e m e th y l g ro u p s .
I n c o n t r a s t , th e melam podin m o le c u le c o n t a i n s c a rb o n .atoms a t t a c h e d
FIGURE 10.
The M olecular C o n fig u r a tio n o f Taraaulipin-A,
t o atom s C4 and CIO a n t i t o e a c h o t h e r and th e e p o x id e oxygen
bonded
t o atoms C2 and C3 i s a n t i t o atom CX5 ( F i g u r e 1 1 ) .
The r e l a t i v e c o n f i g u r a t i o n s found a t t h e
c h ira l c e n te rs are
2S, 6R, and 7S (melampodin 2Rf 6 R, 7 S ) .
These a s s ig n m e n ts con­
form t o t h e a b s o l u t e c o n f i g u r a t i o n p r e d i c t e d by F i s c h e r , b u t
th e a b s o l u t e c o n f i g u r a t i o n was n o t d e te rm in e d e x p e r i m e n t a l l y i n
t h i s stu d y .
I t s h o u ld be p o i n t e d o u t t h a t th e d i f f e r e n c e i n th e
c h i r a l i t y o f atom C2 f o r t h e two m o le c u le s i s c a u s e d by a
d i f f e r e n c e i n th e seq uence a s s ig n m e n ts and sh o u ld n o t be con­
stru e d
as s ig n ify in g a d iff e r e n c e in th e
o v e ra ll c o n fig u ra tio n .
I n b o th m o le c u le s atom s C6 and C7 s e r v e t o l i n k t h e
l a c t o n e sy ste m w i t h t h a t o f t h e t e n membered r i n g and t h e r e i s
c o n s i d e r a b l e s t r a i n a t t h e s e two s i t e s w h ic h i s m a n i f e s t e d i n
th e C6-C7 bond l e n g t h s o f 1 .6 0 (2 ) X i n ta m a u lip in - A and L 5 4 9
(3 ) X i n melam podin.
The n o n - t e t r a h e d r a l a n g l e s a b o u t t h e C7
atom f u r t h e r i n d i c a t e t h e s t r a i n p r e s e n t a t t h i s l o c a t i o n :
C6-C7-C8 1 1 6 .6 (11) and 1 1 7 .0 ( 2 ) ° , C6-C7-C11 9 8 .6 (1 0 ) and
1 0 0 .0 ( 2 ) ° , and C8-C7-C11 1 1 8 .3 (1 3 ) and 1 1 8 .3 ( 2 ) ° f o r
t a m a u lip in - A and melam podin r e s p e c t i v e l y .
The s i g n i f i c a n t d e v i ­
a t i o n o f t h e s e a n g l e s from t h e t e t r a h e d r a l a n g l e 109° 2 8 ' i s
ap p aren t.
An even more d r a m a t i c i n d i c a t i o n o f r i n g a t t a i n i n
t h e s e m o le c u le s i s d i s p l a y e d a t t h e
and
bonds.
The
t o r s i o n a n g l e s f o r t h e p r e s e n t compound a r e summarized i n
T a b le XVI, and t h e v a l u e s o f 1 5 6 .3 ° f o r A^ and 1 6 6 .2 ° f o r A ^ ^ ^
FIGURE 11.
A Comparison Of The S k e l e t a l R ing S t r u c t u r e s Of
Melampodin (Cj^Hj^Ocj) And T a m au lipin-A ( ^ 1 5 ^ 0 ^ 3 ^
MELAMPODIN
CIS
02
03
C4
CI2
C3
01
C2
,CI4
CIO
C8
C7
CI3
C9
TAMAULIPIN -A
168
c a n be s e e n Co d i f f e r ( 6T) from Che u n d ls C o r te d 180° a n g le by
2 3 .7 and 1 3 . 8 ° r e s p e c t i v e l y .
6 T I s a m easu re o f r i n g s t r a i n a t
t h e d o u b le b o n d s , and a p p a r e n t l y t h e r e i s a s i g n i f i c a n t d i s t o r ­
t i o n t h a t t a k e s p l a c e a b o u t t h e s e two bonds i n th e c v c lo d e c a d ie n e
sy stem .
Melampodin g i v e s th e same i n d i c a t i o n o f s t r a i n a t th e s e
two bonds i n t h e v a l u e s o f 1 5 5 .4 (A^) and 4 . 4 ° ( A * ^ ^ ) , and t h e
8 T v a l u e s a r e 2 4 .6 and 4 . 4 ° r e s p e c t i v e l y .
Comparing t h e t o r s i o n
a n g le s f o r t h e s e two compounds, i t becomes a p p a r e n t t h a t t h e 6T
v a l u e s o f 2 3 .7 and 2 4 .6
i n b o th m o l e c u l e s .
o
4
f o r A i n d i c a t e s l a r g e and e q u a l s t r a i n
However, th e 6T v a l u e s f o r A ^ ^ ^
o f 1 3 .8 °
f o r t a m a u lip in - A and 4 . 4 ° f o r melampodin s u g g e s t t h a t t h e s t r a i n
i n th e t r a n s ( ta m a u lip in - A ) c o n f i g u r a t i o n i s g r e a t e r t h a n t h a t
o f th e c i s (ibelampodin) c o n f i g u r a t i o n .
From th e above d i s c u s s i o n o f melampodin and ta m a u l i p i n - A ,
two members o f th e g e r m a c r a n o lid e s e r i e s , we can see t h a t th e same
two l o c a t i o n s o f h e av y s t r a i n o c c u r i n b o th m o l e c u l e s ; a t c a rb o n
4
C7 and a t t h e A bond. The r e a c t i v i t i e s o f t h e i n d i v i d u a l r i n g
system s w ould be p r e d i c t e d t o be s i m i l a r f o r th e t r a n s - t r a n s and
t h e t r a n s - c i s compounds.
However, i n t h e t r a n s - t r a n s s p e c i e s
t h e r e a p p e a r s t o be a d d i t i o n a l s t r a i n a p p l i e d t o t h e r i n g a t t h e
Ai a 0 ) b o n d , a lth o u g h t h e m ag n itu d e o f t h i s d e f o r m a t i o n i s l e s s
4
th a n a t t h e A bond. I n o r d e r t o make t h i s s t u d y c o m p le te ,
r e p r e s e n t a t i v e s from t h e c i s - t r a n s and c i s - c i s ( n o t y e t known)
g ro u p s s h o u ld be s t u d i e d and t h e t o r s i o n s t r a i n m easured t o d e ­
te r m in e i f one o f t h e s e c a t e g o r i e s i s fa v o re d o v e r th e o t h e r s on
th e b a s i s o f s t r a i n i n t h e c y c lo d e c a d ie n e r i n g .
REFERENCES
S. M. Kupchan, T r a n s . N. Y. Acad. S c l . .
(a )
32 . 8 5(1970,
N. H. F i s c h e r , T, J . Mabry and H. B. Kagan, T e t r a h e d r o n .
24, 4 0 9 1 (1 9 6 8 ).
(b)
N. S. Bhacca and N. H. F i s c h e r , Chem. Comm. . 6 8 . (1 9 6 9 ) .
N. H. F i s c h e r , R. W iley and J . D. Wander, J . C. S. Chem. Comm. ,
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F . Sorm, M. Suchy, M. H o lub , A. L in e k , I . H ad in ec and C. Novak,
T e tr a h e d r o n L e t t e r s . 22. 1 8 9 3 (1 9 7 0 ).
" I n t e r n a t i o n a l T a b le s f o r X-Ray C r y s t a l l o g r a p h y , M V ol. 1,
Kynoch P r e s s , Birmingham, E n g la n d , 1965.
G. H. S t o u t and L. H. J e n s e n , "X-Ray S t r u c t u r e D e t e r m i n a t i o n , "
M acM illan C o ., C o l l i e r - M a c M i l l a n L t d . , London, 1970.
S. F . W a tk in s , "ORIENT, DIFSET, and DIFDAT, F o r t r a n IV
P ro gram s f o r t h e IBM 360-65 C o m p u te r," L o u i s ia n a S t a t e U n i v e r s i t y .
M. M. W illia m s (n e ^ C r o z a t ) , "ECALC', A F o r t r a n IV P rogram
F o r t h e IBM 3 6 0 -6 5 C o m p u te r,"
Ph.D . T h e s i s , L o u i s i a n a S t a t e
U n i v e r s i t y , 1974.
P. M ain, M. W. W oo lfson and G. G erm ain, "MULTAN, A Computer
Program F o r The A u to m a tic S o l u t i o n o f C r y s t a l S t r u c t u r e s , "
U n i v e r s i t y o f Y ork, Y ork, E n g la n d , 1971.
EXECXRAY '7 2 Computer S c ie n c e Program com piled by The U n i v e r s i t y
o f M ary lan d , 1972.
171
11.
C. T. G r a i n g e r , A c ta . C r v s t . . A29, 3 8 2 (1 9 7 3 ).
12.
I . L. K a r le and J . R a r l e , A c ta . C r y s t . . 16. 9 6 9 (1 9 6 3 ).
13.
S. F . W a tk in s , N. F . F i s c h e r and X. B e r n a l , P ro c . H a t.
Acad.
S c i . . USA. 7,0. 2 4 3 4 (1 9 7 3 ).
14.
S. N e id le and D. R o g e rs , J . C. S. Chem. Comm. .
1 4 0 (1 9 7 2 ).
VITA
M ich a e l E r n e s t W i t t was b o rn June 1, 1947 I n A ngola, I n ­
d i a n a . He was r a i s e d i n t h e s t a t e o f F l o r i d a ,
U n i v e r s i t y o f F l o r i d a i n Septem ber o f 1965.
and e n r o l l e d a t t h e
Upon g r a d u a t i o n i n
1969 w i t h a B a t c h e l o r o f S c ie n c e d e g r e e i n C h e m istry , he r e c e i v e d
a com m ission i n t h e U n ite d S t a t e s Army.
W hile on a n e d u c a t i o n a l d e fe rm e n t from th e Army, he e n ­
r o l l e d a s a g r a d u a t e s t u d e n t i n Septem ber 1969 a t L o u i s i a n a S t a t e
U n i v e r s i t y i n t h e D ep artm en t o f C h e m istry .
T h e re he s e r v e d a s a
g r a d u a t e t e a c h i n g a s s i s t a n t and r e c e i v e d th e Dupont T e a c h in g
Award i n 1970 f o r h i s m e r i t o r i o u s p e rfo rm a n c e .
I n 1973 he was
a l s o e l e c t e d t o membership i n t h e h o n o r a r y r e s e a r c h s o c i e t y o f
Sigma X i.
The a u t h o r i s a t p r e s e n t a c a n d i d a t e f o r th e d e g r e e o f
D o c to r
o f P h i l o s o p h y in th e f i e l d o f I n o r g a n i c c h e m i s t r y .
He and
h i s w i f e J u d i have b e e n m a r r ie d f o r f i v e y e a r s , and t h e y h ave one
ch ild ,
Andrew B r i a n , and a r e e x p e c t i n g a n o t h e r i n t h e n e a r
fu tu re .
172
EXAMINATION AND THESIS REPORT
Candidate:
M ic h a e l E r n e s t W itt
Major Field:
C hem is t r y
Title of Thesis: The S in g l e C r y s t a l X-Ray D i f f r a c t i o n Study o f S e l e c t e d O rg a n ic
and I n o r g a n ic M o lec u le s
Approved:
Major Professor and Chairman
Dean of the Grami ate School
EXAM INING COMMITTEE:
Date of Examination:
November 29 . 1Q7^