3"7ct
7/8/
SURVEY OF THE SOLID STATE CONFORMATION
OF CALIX[4]ARENES
THESIS
Presented to the Graduate Council of the
University of North Texas in Partial
Fulfillment of the Requirements
For the Degree of
MASTER OF SCIENCE
By
Stephen J. Obrey
Denton, Texas
August, 1997
Obrey, Stephen J., Survey of the Solid State
Conformations of Calixf41arenes.
Master of Science
(Chemistry), August 1997, 173 pp., 39 tables, 33 figures,
references, 86 titles
The characteristics of seventy-six calix[4]arene crystal
structures derived from the Cambridge Crystallographic
Database are presented.
This survey is a discussion of the
inter and intramolecular effects on the solid state cavity
shape and molecular recognition ability of the compounds.
In
addition to this survey, four new calix[4]arene crystal
structures are presented.
The conformational characteristics
of these four calixarenes are determined by a complicated
array of inter and intramolecular interactions in the crystal
packing.
3"7ct
7/8/
SURVEY OF THE SOLID STATE CONFORMATION
OF CALIX[4]ARENES
THESIS
Presented to the Graduate Council of the
University of North Texas in Partial
Fulfillment of the Requirements
For the Degree of
MASTER OF SCIENCE
By
Stephen J. Obrey
Denton, Texas
August, 1997
ACKNOWLEDGEMENTS
The author wishes to express his sincere gratitude to
Professor Simon G. Bott for his guidance, friendship, faith,
and most of all his tolerance.
' My collegues, Phillip Gravelle, Kathlene Talafuse,
William Wolfgong, Janna Smith were my bridge over troubled
waters and I will be forever in their debt
I would like to thank Dusan Hesek from Professor Paul
Beer's research group at Oxford University for providing the
materials used in the X-ray analysis.
A special note of thanks to my "amigos" at the ISB
library for the pleasant manner in which they dealt with such
a troubled individual.
In addition, I wish to thank the Department of
Chemistry, University of North Texas, and the Robert A. Welch
Foundation for financial support.
TABLE OF CONTENT
Page
ACKNOWLEDGEMENTS
ii
LIST OF TABLES
LIST OF FIGURES
viii
ABBREVIATIONS
Chapter
1. INTRODUCTION TO CALIX [ 4 ] ARENES
2 . EXPERIMENTAL
2.1.
Crystallographic Data for Calix[4]arenes
2.2.
X-ray Crystallography
1
8
8
10
3. SOLID STATE CONFORMATION OF CALIX[4]ARENES
WITH INTRAMOLEULAR HYDROGEN BONDING
15
3.1.
Introduction
15
3.2.
Tetrahydroxycalix [ 4 ] arenes
16
3.3.
Tr ihydroxycalix [ 4 ] arenes
31
3.4.
1, 2-dihydroxycalix [4] arenes
3.5.
1,3 -dihydroxycalix [ 4 ] arenes
39
3.6.
Monohydroxycalix [ 4 ] arenes
46
32
4. SOLID STATE CONFORMATION OF CALIX[4]ARENES
WITHOUT INTRAMOLEULAR HYDROGEN BONDING
4.1.
4.2.
4.3.
4.4.
Introduction
Tetraalkylated Calix[4]arenes in
the "Cone" Conformation
Tetralkylated Calix[4]arenes with
Small Lower Rim Substitutents
Tetraalkylated Calix[4]arenes in
the "Partial Cone" Conformation
52
52
53
60
66
4.5.
4.6.
Tetralkylated Calix[4]arenes in
the "1, 2-Alternate" Conformation
Tetraalkylated Calix[4]arenes in
the " 1, 3-Alternate" Conformation
4.7
72
Conclusions
5. CRYSTAL STRUCTURES OF NEW CALIX[4]ARENES
74
79
81
5.1.
Introduction
81
5.2.
Structure 1
82
5.3.
Structure II...
91
5.4.
Structure III..
98
5.5
Structure IV
103
5.6.
Conclusion
Ill
APPENDIX A
114
APPENDIX B
123
APPENDIX C
135
APPENDIX D
147
APPENDIX E
REFERENCES
162
LIST OF TABLES
Table
1
2
3
4
5
6
Page
General representation of tetrahydroxy
calix [ 4 ] arenes
Mean Molecular plane angles of structures
la - g
18
The cavity guests found in structures
la - g
19
Molecular plane angles of structures
lh and li
20
Molecular plane angles of structures
lj and lk
22
Molecular plane angles of structures
iq
7
17
- t
24
Molecular plane angles of structures
11 - n
26
Molecular plane angles of structures
lo andlp
28
9
Molecular plane angles of structure lu
30
10
General representation of 1,2-dihydroxy
calix [4] arenes
33
Molecular plane angles of structures
2a and 2b
35
Molecular plane angles of structures
2c and 2d
37
8
11
12
13
General representation of 1,3-dihydroxy
calix [ 4 ] arenes
14
Molecular plane angles of structures
3a - £
15
Molecular plane angles of structure 3h
16
General representation of monohydroxy
calix [4 ] arenes
40
42
47
17
Molecular plane angles of structures
4b and 4c
18
Molecular plane angles of structure 4a
19
General representation of tetralkylated
calix[4]arenes in the "cone" conformation
Desriptive plane angles for symmetric and
assymetric "cone" conformations
20
21
46
50
54
55
Molecular plane angles for structures
5q and 5r
56
Mean conformation of calixarens with
small para substituents
58
23
Molecular plane angles for structure 5s
59
24
General representation of tetrasubstituted
calix[4]arenes with small lower rim
substituents
61
Mean conformation of "partial cone"
structures
62
General representation of tetralkylated
calix[4]arenes in the "partial cone"
conformation
67
Molecular plane angles for structure
7a and 7d
66
Molecular plane angles for structures
7b and 7c
69
General representation of tetralkylated
calix[4]arenes in the "1,3-alternate"
conformation
75
30
Molecular plane angles for structure 9b
76
31
Molecular plane angles for structures
9a, 9c, 9d and 9e
78
X-Ray Crystallographic collection and
processing data for structure 1
83
22
25
26
27
28
29
32
33
34
Molecular plane angles for structure X
and mean plane angles for similar
1, 3-dihydroxy calix[4] arenes
X-Ray Crystallographic collection and
87
processing data for structure II
35
36
37
38
39
Molecular plane angles for structure II
and mean plane angles for similar
1, 3-dihydroxy calix[4] arenes
X-Ray Crystallographic collection and
processing data for structure III
Molecular plane angles for structure III
and mean plane angles for similar
1, 3-dihydroxy calix [4] arenes
92
93
100
102
X-Ray Crystallographic collection and
processing data for structure IV
105
Molecular plane angles of structure IV
106
LIST OF FIGURES
Figure
1
page
General Representation of Calix[4] arenes
1
2
Four Conformations of calix[4]arenes
3
3
Crystal strucutre of p-t-butyl calix[4]arene:
toluene clathrate.
5
4
5
6
7
8
Crystal structures of the cage complex of
lh and 11
21
Diagram of the trimer and molecular
geometry of structures lj and lk
23
Diagrams showing the inter-calixarene
inclusion complexes in lq - It
25
Crystal packing diagrams showing it - n
interactions in structures 11 - In
27
Diagrams of the molecular geometry of
structures lo and IP
29
9
Molecular geometries for structures
2 a and 2b
10
Diagrams of the intermolecular inclusion
observed in 2a
11
Molecular geometries for structures
2c and 2d
12
Molecular geometries for structure 3h
43
13
Crystal packing, molecular geometry and
plane angles for structure 3i
Molecular geometries for structures
4b and 4c
45
48
Molecular geometries for structures
5r and 5q
57
Crystal packing and molecular geometry
for 6g
64
14
15
16
17
Molecular geometries for structures
7a and 7d
68
Molecular geometries for structures
7b and 7c
70
General representation, table of plane
angles, and molecular geometry of 8a
73
Molecular geometries for 9a, 9c,
9d, and 9e
77
General representation of compounds I, II,
III, and IV
81
ORTEP diagram of structure I with
thermal ellipsoids drawn at 50%
probability level. H atoms are
omitted for clarity, (side view)
85
ORTEP diagram of structure I with
thermal ellipsoids drawn at 50%
probability level. H atoms are
omitted for clarity, (topview)
86
Diagram of the crystal packing for
structure I
89
A diagram of the unit cell of
s true ture I
90
ORTEP diagram of structure II with thermal
ellipsoids drawn at 50% probability level.
H atoms are omitted for clarity
94
ORTEP diagram of structure I with thermal
ellipsoids drawn at 50% probability level.
H atoms are omitted for clarity. Hydrogen
bondng interaction between 01b and the
THF molecule
96
28
A diagram of the unit cell for structure II
97
29
ORTEP diagram of structure III with
thermal ellipsoids drawn at 50% probability
level. H atoms are omitted for clarity, (side
view)
18
19
20
21
22
23
24
25
26
27
30
101
A diagram of the unit cell for structure III,...104
31
ORTEP diagram of structure IV with thermal
ellipsoids drawn at 50% probability level
H atoms are omitted for clarity
107
32
A diagram of the unit cell for structure IV. ...109
33
A diagram of the unit cell for structure IV. ...110
ABBREVIATIONS
THF
tetrahydrofuran
CHAPTER 1
INTRODUCTION TO CALIX[4]ARENES
Calixarenes are a class of cyclic bowl-shaped organic
macrocycles that have become of interest over the last 25
years.1 The general structural representation of a calixarene
is shown below
Figure 1. General representation of calix[4]arenes
The general term "calix[n]arene"2 is used to describe the
calixarenes where "n" describes the ring size which is most
commonly 4, 6, or 8,3 although other oligomers have been
reported.4
Much like crown ethers,5 and cyclodextrins,6 calixarenes
posses large cavities that make them potential hosts for
molecular recognition chemistry. Unlike cyclodextrin and
crown ethers, calixarenes are readily functionalized on the
upper and the lower rim of the macrocyles and the presence of
methylene linkages allow rotational flexibility which makes a
variety of conformations possible. Due to these
functionalization and conformational properties, calixarenes
may be "chemically tailored" for application as potential
host-guest sites,7 catalyst supports,8 and transport agents
for the extraction of metals from aqueous media.9
Calixarenes may be readily functionalized at both
the phenolic oxygen (R), commonly known as the lower rim, and
at the para position (R1), known as the upper rim.
Synthetic
chemists have developed methodology for selective lower rim
substitution of calix[4]arene for mono-alkylation,10 dialkylation11 and trialkylation.12
There is also methodology
for asymmetric upper rim substitution with a variety of
substrates.13
One of the requirements to use these compounds for
molecular recognition is to produce and maintain a stable
cavity shape and size to accommodate a guest.14 The rotational
flexibility about the methylene bridges allow calix[4]arenes
to adopt and maintain four different geometries based on the
relative orientation of the rings.15
These conformations are
commonly known as the "cone", "partial cone", "1,2-alternate"
and the "1,3-alternate" conformations.16
The "cone"
conformation involves all four aromatic rings being oriented
in the same direction. The "partial cone" has three rings
pointing up with the fourth ring down. Both the "1,2alternate" and the "1,3-alternate" have two rings up and two
down in different isomers.
Cona
h r t t a l COM
L,J-UUrn»U
1,3-AIUrnaU
Figure 2. The four conformations of calix[4]arenes
The "1,2-alternate" has the two adjacent rings pointed down
and the other two pointed up. The "1,3-alternate" has the two
opposing rings up and the other two down.
Synthetically, the
conformation of a functionalized calixarene is most commonly
controlled utilizing a template effect related to the nature
of the cation used during alkylation.17
These conformations
should only be treated as idealized orientations of the rings
and actually give no indication as to the cavity shape, size,
or the relative angles the aromatic rings.
The specific
characteristics of the aromatic rings are dependent on the
functionalization of the upper and lower rim, the
conformation in which the calixarene was synthesized, and a
series of complicated inter and intramolecular interactions
One of the most common ways in which to produce a stable
conformation is the introduction of sterically bulky
substitutents attached to the lower rim phenolic oxygens.
It
is well documented that only substituents smaller than propyl
may have the rotational freedom to allow the interconversion
between one conformation to another.18
Ethyl substituents
show the ability to undergo this conformational mobility at
elevated temperatures, but do not readily interconvert at
room temperature.19
In application to single crystal X-ray
crystallography, it is important to note that, since most
crystals used are grown at or below room temperature, we may
only treat groups that are smaller than ethyl as
conformationally mobile for analysis of the solid state
structures.
In 1979, Adreetti et al. published the crystal structure
of the inclusion complex between para t-butyl calix[4]arene
and toluene shown in Figure 3.20 This crystal structure shows
the calixarene in the "cone" conformation with C4V symmetry.
This conformation is maintained by the cyclical network of
hydrogen bonds on the lower rim of the calixarene, which
holds the aromatic rings so that they form a cavity or a
bowl.
This cavity contains one toluene molecule as a guest
which is oriented so that the methyl group is pointed into
the cavity.
Although the positions of the hydrogen atoms on
the guest toluene were not located, it is believed that the
methyl hydrogens are interacting with the 7t-cloud of the
aromatic rings.
Figure 3. Crystal strucutre of p-t-butyl calix[4]arene:
toluene clathrate
The para-t-butyl groups also show CH3-7C interactions with the
aromatic ring of the toluene.
These CH3-71 interactions are
among the most common observed for the host guest complexes
of calixarenes with neutral guest molecules.
Since this publication, there have been many studies on
the inclusion behavior of calixarenes.21
Due to the fluxional
behavior of calixarenes in solution there is little evidence
for solution state inclusion complexes,22 therefore solid
state analysis by using single crystal X-ray diffraction is
the most common way to analyze these interactions.
Recently,
it has been shown that the inclusion behavior of these solid
state complexes may also be analyzed by
13
C Cp-MAS NMR
experiments but only in combination with X-ray
crystallographic data.23 I n
the solid state#
calixarenes have
Shown the ability to form inclusion complexes with other
neutral organic molecules such as xylene, anisole,
acetonitrile, acetone, chloroform, methylene chloride as well
as other neutral organic molecules.
In addition to this
host-guest behavior, calixarenes are also capable of
retaining guest species in channels and layers within the
crystal lattice.
These channel guest species make
calixarenes particularly difficult to analyze by X-ray
diffraction since these crystals tend to lose the solvent and
decompose readily.
A previous analysis of calix[4]arene crystal structures
was undertaken by Lipkowitz in 199324 i n an attempt to
determine their architectural foundation for use with
computational modeling programs.
In this paper a total of 29
crystal structures of calixarenes in the "cone" conformation
were analyzed, none of these contained metals or bridging
linkages between the phenolic units.
These were partitioned
into three categories: native structures, near-native
structures, and derivatized structures. Native strucutres are
unsubstituted on the lower rim with either H, Me or t-buytl
substitutents in the para position. Near-native structures
also have H, Me, or t-butyl in the para position but the 4-OH
groups are replaced by a simple functionality like ethers or
esters.
Derivatized calixarenes are also substituted on the
lower rim and include all para substituents other than H, Me,
or t-butyl.
Although this paper reports in detail the
important bond lengths, bond angles, and dihedral angles, it
fails to describe the effect of these substituents on the
cavity formed by the four aromatic rings.
In the first part of this thesis, I will describe the
inter and intramolecular effects which alter the cavity
shape, size, and inclusion properties of various types of
calixarenes.
The second part of this thesis contains a
disscussion of four new calix[4]arene crystal structures
which add to the limited body of knowledge concerning the
solid state complexes.
CHAPTER 2
EXPERIMENTAL
2.1.
Crystallographic Data for Calix[4]arenes
All data used in the survey of crystal structures of
Calix[4]arenes were obtained using the 1996 Cambridge
Crystallographic Database.25
Of the two hundred thirty eight
hits, ninety eight were applicable to the work, (the rest
being either higher homologs, contained metal atoms or
bridging linkages)
Of these 98 remaining structures, twenty-
four had no coordinates, incomplete coordinates, or were
disordered.
These were thus removed. This left a working set
of 76 calix[4]arenes.
These structures were partitioned into ten categories.
Five m
which the conformation is determined by the presence
of intramolecular hydrogen bonding between the phenolic
units.
These five categories are the tetrahydroxy
calix[4]arenes, trihydroxy calix[4]arenes, 1,3-dihydroxy
calix[4]arenes, 1,2-dihydroxy calix[4]arenes, and monohydroxy
calix[4]arenes.
The other five were separated by
conformation and size of the lower rim substituents.
The
first category was defined as tetrasubstituted calix[4]arenes
with lower rim substitutents which allow conformational
freedom.
The other four categories were calixarenes which
are frozen in the "cone", "partial cone", 1,2-alternate", and
the "1,3-alternate"
conformations.
For each of the 76 crystal structures, twelve pieces of
data was collected using the 3D-structural option in the CCD.
Six of these were distances between lower rim oxygens.
The
four distances between adjacent oxygen atoms may be used to
indicate the location of intramolecular hydrogen bonding
interactions.
The two transannular oxygen-oxygen distances
give an indication as to the shape of the lower rim of the
cavity.
The other six pieces of data were plane angles.
The
first four were the angles that each aromatic plane made with
the mean plane of the methylene carbons which reflect the
canting angle of the aromatic rings with the mean plane of
the methylene carbons.
These plane angles were normalized
for each structure so that if the angle is less than 90
degrees, the top of the ring is pointed away from the cavity
and if the angle is greater than 90 degree the top of the
ring is pointed into the cavity.
The other angles were
between the two opposite aromatic planes.
These plane angles
may be used to describe the shape of the calixarene cavity
which may allude to the presence of host-guest interactions.
All plane angles, oxygen-oxygen distances and the database
codes accumulated in this search are listed in Appendix A.
Each of these twelve data points were reported from the CCD
with three significant figures past the decimal point.
Since
10
these values are not truely reflective of the accuracy X-ray
diffraction, the angles will be truncated at one digit past
the decimal place and the distances will be truncated after 2
decimal places,
it is important to realize that these values
are not from the crystal structure data but in fact generated
by the CCD, by treating the atom as a single point rather
than a sphere or an ellipsiod. All means reported were
statistically analyzed at the
t0.005 probablity level to
assure the statistical relavance of the data set.
it is
important to note that due to the small sample size used in
the calculation of the means, these values may not be
representative of the population. All crystallographic
figures were generated using PLUTO.26
2.2.
X-ray Crystallography
X-ray crystallography may provide the most useful
information regarding the structure of a complex furnishing
information about bond lengths and angles as well as
connectivity. Unfortunately, there are several drawbacks to
its application.
The most obvious problem is that one needs
a single crystal that is at least 0.1 mm in every dimension.
Some systems do not crystallise, and even if crystals can be
obtained, they may not be of sufficient size or quality.
Even if one manages to obtain a crystal, there is no
guarantee that it represents the bulk of any precipitate,
much less the predominant species in solution.
11
In cases where thermally stable crystals were obtained,
they were mounted in thin glass capillaries with silicone
grease by one of two methods. Where solvent-dependent
crystals were obtained, the lattice depletion was overcome by
addition of mother liquor or fresh solvent to the capillary
tube. The ends were plugged with modelling clay and then
sealed with an oxygen-methane torch as soon as possible.
Crystals that were not solvent dependent were mounted on the
bench top with the use of a microscope.
In the cases where
thermally unstable crystals were obtained, they were mounted
on a glass fiber using Paratone-n. The crystal was held in
place by passing a cold (-60 °C) stream of nitrogen across
the crystal.
A suitable crystal was selected and mounted on the
goniometer head of an Enraf-Nonius CAD-4 automated
diffractometer which comprised of a four-circle kappa axis
goniometer with graphite crystal monochromated Mo radiation
(A,=0.71073 A ) .
The crystal-to-detector distance was 173 mm,
and the take-off angle was 5.6 degrees. The diffractometer
was controlled by a Digital Corporation VMStation 3100/76.
The crystal was first centered visually under the
diffractometer microscope and then the program SEARCH27 was
run to find up to 25 reflections and measure their angular
settings.
These were then used by the INDEX27 routine to
calculate the primitive unit cell, where appropriate this
was transformed, either to a higher symmetry or to fulfil
12
international conventions.28 Strong axial reflections were
accurately centered and then used to refine the cell
parameters.
Where the cell was reasonable and did not bear close
resemblance to that of structures previously determined, data
was collected.
scan ( m
This was performed using either a co-20 or co
cases where a cell axis was greater that ca. 20 A )
technique with a variable scan width as given in Eq. 2-1 (A
was between 0.65 and 0.8 degrees).
Scan Width = A + 0.35 tan (0)
(2-1)
Backgrounds were measured by extending the calculated
width on either end of the scan by 25%.
A fixed vertical
detector aperture (4 mm) and a variable horizontal aperture
(3 + tan 0) were used.
Every reflection was subjected to a
prescan at a rate of 8 degrees per min.
Reflections with
I/ct(I) <2 for this prescan were rejected as weak, and those
for which i/<r(i) > io were accepted immediately.
Reflections
not falling into these two categories were rescanned at
speeds ranging from 0.67 to 8 degrees per min for up to 120 s
in an attempt to increase I/a(I) to 10.
Three reflections
were measured every 3600 s of exposure time to monitor
crystal decay.
Crystal alignment was checked using the same
reflections every 250 data points, and if the scattering
vectors deviated by greater than 0.10 degrees from their
13
calculated values at any stage, the unit cell and orientation
matrix were recalculated.
The intensity (I) and standard deviation [a(I)] were
calculated using Eqs. 2-2 and 2-3, respectively, where C is
the total number of integrated counts, B is the sum of the
left and right backgrounds, A is an attenuator factor (either
1 or 14.3), and S is the scan rate.
I = AS(C - 2B)
(2-2)
a(I)=AS(C + 4B)l/2
(2-3)
All computations were carried out on a DEC VAXStation
3100/76.
Calculations, except where noted, were performed
using MolEN crystallographic software package.29 The
structures were solved using direct methods
or SHELXS-8632) and difference Fourier maps.
(MULTAN,30
siR,31
After
refinement of the entire model with isotropic thermal
parameters, a Fourier absorption correction (DIFABS)33
applied.
was
The extent of conversion of certain atoms to have
anisotropic thermal parameters was dependent upon the quality
and number of data.
Hydrogen atoms were either located or
generated and allowed to ride on the appropriate attached
atom [U(H) = 1.3 Ueq(Attached atom)].
during refinement was Zw(|F0| - |FC|)2
[(OFo)2
-
0.04F
2
o
]1/2.
The function minimized
where
the weight, w =
14
The results of the final refinement are reported as
three parameters: (1) R = (X(|F01 - fFc|)/ Z<|F0|), (2)
[wZ(|F 0 | - |F C |) 2 /wX(|Fq|)2]l/2
a n d
(3) goodness-of-fit
Rw
=
(GOF)
= [Zw(|fq| - 1Fc|)2]/(number of reflections - number of
least-squares parameters).
Crystallographic diagrams were drawn with the aid of
ORTEP-Il34_
Scattering factors and corrections for the real
and imaginary components of anomalous dispersion were taken
from reference 28.
CHAPTER 3
SOLID STATE CONFORMATION OF CALIX[4]ARENES
WITH INTRAMOLEULAR HYDROGEN BONDING
3.1. Introduction
Hydrogen bonding is commonly believed to be the single
strongest interaction in the solid state35 an d therefore has a
major effect on the conformation of calix[4]arenes.
Calixarenes that undergo intramolecular hydrogen bonding
interactions are subdivided into five categories dependent on
the presence and location of alkyl substitutents on the
phenolic oxygens.
Introduction of alkyl substituents on the
lower rim of the calixarene changes the nature of the
intramolecular hydrogen bonding by the alteration of an
alcohol into an ether. This introduction of an ether carbon
from 0-alkylation also requires the calixarene to adjust its
conformation to accommodate the increased steric bulk. Due to
selective asymmetric alkylation of calix[4]arenes there are
five types of calix[4]arenes that may contain intramolecular
hydrogen bonding: tetrahydroxycalix[4]arenes, trihydroxycalix[4]arenes, 1,2-dihydroxycalix[4]arenes, 1,3-dihydroxycalix[4]arenes, and monohydroxycalix[4]arenes.
Although the
16
intramolecular hydrogen bonding affects the gross geometry of
the calixarene cavity, the fine structure is affected by a
series of complicated interactions in the crystal packing.
This part of the survey describes the characteristics of
these five structurally different calixarenes and some of the
inter and intra molecular effects directing the observed
conformation.
3.2. Tetrahydroxycalix[4]arenes
The search of the CCD resulted in twenty-one crystal
structures that fall into the tetrahydroxy calix[4]arene
category. The chemical representation of these twenty-one
calixarenes is shown in Table 1. All of these calixarenes
crystallise in the "cone" conformation due to the presence of
a strong hydrogen bonding network formed by the four phenolic
alcohols on the lower rim of the calixarene. The mean
adjacent oxygen oxygen distance was 2.65 A for all twenty-one
crystal structures which is indicative of a strong hydrogen
bond. The cavity shape of tetrahydroxycalix[4]arenes appears
to be directed by the intermolecular and intramolecular
interactions in the crystal packing.
Intermolecular interactions observed in these calixarene
crystal structures are due to inclusion of a neutral organic
guest m the cavity, inclusion of a para substitutent of an
adjacent calixarene, or from n - stacking from para
substituents with aromatic rings. All of these
17
Table 1. General representation of tetrahydroxycalix[4]arenes
I1
r ™A
I
/ \
M'
=
\
?
H
I
M
R2
J(_/
HO—>
y-OH
•
VM
II
R3
M=H
Compound
la
lb
lc
Id
la
If
Iff
lh
11
lj
lk
11
lxn
In
lo
IP
Compound
la
lr
Is
It
Compound
lu
R1=R^=P7=PA
t-butyl
hydroxyethylpiperazine
1,1,3,3-tetramethylbutyl
isopropyl
H
H
isopropyl
t-butyl
isopropyl
H
H
phenyl
phenylazo
4-nitrophenylazo
1,1,3,3-tetramethylbutyl
ethyl
H
octyl
isopropyl
t-butyl
_E2_
H
methyl
isopropyl
nitro
R1=R2=R3=R4
H
H
octyl
isopropyl
t-butyl
M
methyl
Referenrp
20
36
37
38
39
40
41
42
38
39
40
41
42
43
37
44
_SiL
bromopropyl
methyl
isopropyl
methyl
Reference
45
46
38
47
Reference
48
18
intermolecular interactions may be observed in the crystal
packing diagrams.
The intramolecular interactions observed
in tetrahydroxy calixarenes involve the self-inclusion of the
psra substituents or introduction of meta substituents that
interact with adjacent aromatic rings of the calixarene.
There are eleven, la - k, crystal structures of
tetrahydroxy calix[4]arenes where the shape of the calixarene
cavity is affected by inclusion of a neutral organic
molecule.
There are three different crystallisation patterns
observed which are dependent on the number of calixarenes per
guest molecule.
There are seven examples, la - g, of tetrahydroxy
crystallising with one neutral organic guest in the cavity of
a single calixarene.
with the exception of this host-guest
interaction, these compounds show no unusual interactions in
the crystal packing so the geometry of the cavity should be
solely determined by the guest present.
diagram of the mean geometry and
Table 2 presents a
plane angles for these
seven structures.
Table 2.
Plane
A
B
C
D
A - C
B - D
Mean molecular plane angles of structures la - g
Degrees
55.1
55.0
55.8
55.8
68.7
68.4
19
These seven crystal structures are very close to c 4 v
symmetry.
Each of the four aromatic rings make angles close
to 55 degrees with the methylene carbons.
The interplanar
angles between two opposite planes are close to 69 degrees.
The nature of the para substituent does not seem to affect
the cavity shape and size, but does have an affect on the
interaction with the guest molecule.
In these seven
structures there are five different guest molecules observed:
toluene, xylene, acetone, acetonitrile, and l-(2hydroxyethyl)piperazine.
Table 3 shows the guests that are
included in each of these seven structures.
Table 3. The cavity guests found in structures la - g
Structure
Ik
^
Iff
Guest
toluene
1-(2-hydroxyethyl)piperazine
toluene
xylene
acetonitrile
acetone
toluene
Each of these guests orients itself in the cavity to allow CH
71 xnteractions with the aromatic rings of the calixarene.
The two aromatic guests, toluene and xylene, each show the
presence of CH - it interactions with the para substituent.
In all cases, this guest is disordered so that each of the
20
four aromatic rings interacts with the guest in a symmetric
manner.
There are two examples, lh and li, of cage complexes
where two calixarenes play host to a single neutral organic
guest molecule.
The two calixarenes are oriented so that the
upper rim of each calixarene is facing one another with the
guest molecule being trapped in the middle.
Figure 4 shows
these two calixarenes with the guest in the middle.
Table 4
shows the relevant angles for the aromatic rings in these two
structures.
Table 4.
Molecular plane angles of structure lh and li
Plane
£•
®
£
~
a
B
£
B
D
lh
54 2
54 2
55
-2
55 2
*
71 7
*
71
-7
ii
55.8
55.8
55.8
55.8
68 4
68.4
Although both the calixarenes are intimately joined,
there appears to be no structural deviations of the
individual calixarene molecules as a result of this close
interaction.
The observed conformation is very similar to
the previously mentioned structures of one calixarene with a
single guest molecule. All four of the aromatic rings are
inclined close to 55 degrees and the interplanar angle
between two alternating aromatic rings is close to 70 degrees
21
Structure of Hi
<->
Structure of li
Figure 4.
II
Crystal structures of the cage complex of Uh. anij
22
m
both cases. The guest included in the cage is disordered
in both structures, the anisole in lh is disordered over 8
positions and the xylene in li is disordered over 2
positions.
The disorder of the guest molecule allows it to
interact with the cavity in a symmetric manner.
There are two examples, lj and lk, of cage complexes
where three calixarenes play host to a single organic guest
molecule.
Figure 5 shows the trimer and a representation of
a single molecule.
Table 5 shows the plane angles of the two
calixarene molecules.
Table 5.
Molecular plane angles of structure lj and lk
Slmm
£
®
n
A - P
R ~ Dn
B
65
li
lk
• 71
64.5
42.7
42-
5o" 7
I
64
•7
•7
50 8
4 .-
42
95.8
9
6
The crystal packing diagram shows that these calixarenes
crystallise as a trimer with the single guest molecule in the
center of the complex.
Each calixarene has one aromatic ring
that interacts with the cavity of the adjacent calixarene.
Due to the asymmetric nature of this interaction there is a
structural deviation observed in the cavity.
Two of the
aromatic rings fold up toward the center of the cavity making
an mterplanar angle of about 50 degrees.
The other two
23
Diagram of the trimer for Structures lj anH
Representation of the molecular geometry from structures lj
and lk
Figure 5.
Diagram of the trimer and molecular geometry of
structures lj and lk
24
rings fold, down away from the center of the cavity making an
interplanar angle of about 95 degrees.
The structural
deviation observed in this compound may be explained by the
asymmetric way in which one of the calixarene rings interacts
with the adjacent calixarene cavity.
There are four compounds, lq - t, which show
intermolecular interactions of the para substituent of one
calixarene interacting in the cavity of another calixarene.
These interactions may be observed in the crystal packing as
seen in Figure 6.
Table 6 shows the canting angles of the
aromatic rings for the individual molecules in the structures
Table 6.
Plane
A
B
c
D
A
B
~ C
" D
Molecular plane angles of structures lq - t
is
61.4
52.3
57.8
57.8
60.9
74.9
lr
55.4
56.3
58.5
53.9
66.1
69.8
is
55.0
50.4
53.8
53.3
71.2
76.3
it
56.1
48.8
53.6
55.5
70.4
75.7
The conformation of the calixarene cavity in the four
structures is very similar to the previously mentioned
calixarenes with C4v symmetry.
The shape of the calixarene
cavity is slightly deformed with two of the alternate
aromatic rings folding slightly further out.
Each of the
four structures has different substituents interacting in the
cavity and therefore the geometry is effected differently.
25
iq
Is
lr
It
Figure 6. Diagrams showing the inter-calixarene inclusion
complexes in lq - It
26
The minor deformation may be attributed to the asymmetric
manner in which the guest resides in the cavity.
There are three crystal structures, 11 - n , of compounds
with para substituents that contain aromatic rings. Figure 7
shows the crystal packing diagrams for these three compounds
and their structural representation.
Table 7 lists the plane
angles f oir these thiree ca-lixoxenes.
Table 7.
Molecular plane angles of structure 11 - n
11
2
B
J?*®
D
ll't
55 5
•
70 4
75 7
-
*
„
» " DS
aI'I
51
57 -
In
-°
4
66
-°
49
-°
64
-6
58.4
79.5
34.5
6
6.0
34 5
48 1
in.'o
The crystal packing diagrams for these three compounds, in
Figure 7, shows the presence of % - stacking between the para
aromatic substitutents. The manner in which this occurs is
similar to inter-calixarene inclusion where the para
substituent on an adjacent calixarene interacts with the
cavity of the calixarene.
In addition to the presence of the
n- stacking interaction each of these calixarenes acts as a
host to a neutral guest molecule.
Due to the complicated
nature of these intermolecular interactions, direct
correlation of these effects to the calixarene geometry would
be unfounded.
27
Crystal packing diagram for In
Crystal packing for 11
Crystal packing for 1m
Figure 7.
Crystal packing diagrams showing K-K interactions
in structures 11 - in
28
There are two crystal structures, lo and lp that show no
xntermolecular interactions in the crystal packing but rather
have intramolecular interactions with two para substituents
interacting within the cavity. As can be seen in Figure 8,
two of the para substituents fold into the cavity effectively
blocking the cavity from inclusion of a guest molecule.
The other two para substituents fold out of the cavity
and show no effect on the cavity conformation.
The crystal
packing of these two compounds shows a minimal amount of
intermoiecular interactions therefore the cavity shape may be
attributed to only intramolecular interactions.
Table 8
lists the angle of the aromatic planes with the methylene
carbons and the interplanar angles between the two alternate
aromatic rings.
Table 8.
Molecular plane angles of structure lo and lp
Plane
58
B
r
D
a
r
B
~
n
B
°
-4
52 1
58 7
56 4
62 8
*
71.5
1J2
56.0
53.0
59.8
55.7
64.2
71.1
Compared to the mean values for calixarenes with a
single organic guest within the cavity there is a slight but
noticeable deviation in rings A and C that corresponds to the
aromatic rings with para substituents folding into the
29
Molecular geometry of lo
Molecular geometry of lp
Figure 8. Diagrams of the molecular geometry of structures
lo and lp
30
cavity.
Planes B and D appear to maintain a similar angle to
other tetrahydroxy compounds.
Introduction of a substituent in the meta position
effectively changes the shape of the calixarene cavity.
There is one example, lu, of tetrahydroxy calixarene with
meta substituents.
Table 9 shows a representation of lu and
its associated plane angles.
Table 9. Molecular plane angles of structure lu
Plane
A
B
C
D
A - C
B -D
21.6
69.2
25.6
132.8
Analysis of the cavity shape of lu demonstrates that
introduction of meta-methyl groups has significantly
distorted the conformation of the cone due to steric
repulsion between the meta methyl substituent and the
adjacent aromatic ring. This compound does not show the
presence of a guest within the cavity since the pinching of
two of the aromatic rings make inclusion sterically
prohibitive.
The presence of the four hydrogen bonding sites on the
lower rim of the calixarene directs the "cone" to be the
preferred conformation in the solid state. Conformationally
31
all of these structures have similar cavity geometries with
the only major distortion due to intramolecular interaction
from meta substituents and intermolecular it - stacking.
With
the exception of the two crystal structures where the upper
rim para substituents fold in and block the cavity and
calixarenes with meta substituents, all the tetrahydroxy
calix[4]arenes show the presence of a guest within the cavity
being held by CH - it interactions with the aromatic rings.
3.3. Trihydroxycalix[4]arenes
Monosubstituted calixarenes have three hydroxyl groups
and one ether oxygen on the lower rim.
The replacement of
one of the phenolic hydrogens with an alkyl substituent
significantly reduces the strength of the overall hydrogen
bonding network but these interactions still maintains a
sizeable effect on the conformation. Although there are no
crystal structures of monoalkylated calixarenes, there have
been several synthesised in the literature.28 % NMR analysis
of these compounds shows that the "cone" conformation is
observed almost exclusively.
Further analysis into the -solid
state characteristics of this family of calixarenes should be
investigated to understand the affect of the breaking one of
the hydrogen bonds and the manner in which the calixarene
adjusts its conformation upon the introduction of a single
ether linkage. Additionally these compounds should also show
32
host-guest properties similar to the tetrahydroxy
calix[4]arenes.
3.4.
1,2-dihydroxycalix[4]arenes
Four of the crystal structures from the CCD search are
1,2-dihydroxy calix[4]arenes.
Table 10 shows the generic
representation of these four calixarenes.
The presence of
the two hydroxy1 substituents on the lower rim directs the
conformation of the calixarene.
These two hydroxyl
substituents make two hydrogen bonds, one of which is always
bonded to the other hydroxyl group which in turn interacts
with the adjacent phenolic ether oxygen.
This orientation
assures that three of the aromatic rings will be syn and the
fourth ring may be either syn or anti dependent on the manner
in which the calixarene was synthesised.
If both the
substituted rings are syn the expected conformation is a
cone", but if they are anti the "partial cone" results.
Compounds 2a and 2b were synthesised so that the two
lower rim substituents are syn. Since the size of these
substituents do not allow them to rotate they have a fixed
orientation and both crystallise in the "cone" conformation.
Figure 9 shows the representation of the solid state
structure for these three compounds.
Table 11 shows the
relevant plane angles for these compounds.
The structure 2a has two inequivalent calixarenes in the
assymetric unit.
Structure 2a (A) has two hydrogen bonds,
33
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Oi O H O
^ in in H
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34
Molecular Geometry of 2b
Molecular geometry of the two inequivalent molecules in
structure 2a
Figure 9. Molecular geometries for structures 2a and 2b
35
one between the adjacent phenolic oxygen and a second with
the ethyl ether oxygen on the lower rim substituent of the
adjacent aromatic ring.
Table 11.
Molecular plane angles of structure 2a and 2b
Plane
£
2a (A)
87 5
35.1
78.8
40.8
13.7
75.8
B
C
D
A
" C
B - D
2a (B)
75.6
46.0
60.3
51.5
54 1
97.5
2b
60.5
61.9
68.9
53.0
50.6
65.0
The presence of this unusual hydrogen bonding interaction
Pr®vents inclusion of a guest within the cavity of this
calixarene.
Strucuture 2a (B) has the expected hydrogen
bonding network with the hydrogen bonds only between the
phenolic oxygens.
The symmetrical arrangement of the four aromatic rings
in 2b and 2a (B) provides a cavity for inclusion
interactions.
m
2b has an ethanol molecule acting as a guest
the cavity and 2a (B) shows an intermolecular interaction
with an adjacent calixarene.
The inter calixarene inclusion
may be seen in the crystal packing in Figure 10.
Compounds 2c and 2d were synthesised so that the two
substituted aromatic rings have an anti arrangement with
lower rxm substituents large enough to prevent conformational
interconversion. Due to the anti arrangement of the two
36
Figure 10.
in 2a
Diagram of the intermolecular inclusion observed
37
substituted aromatic rings both of these compounds
crystallise in "partial cone" conformation. Figure 11 shows
the solid state conformation of these two compounds.
Table
12 shows the plane angles associated with these two
compounds.
Table 12.
Molecular plane angles of structure 2c and 2d
Plane
A
B
C
D
A - C
B - D
2c
-67.0
73.5
48.8
58.0
18.7
48.4
2d
-68.9
73.3
39.2
66.4
28.9
40.3
These two structures have similar conformational
characteristics.
The aromatic rings that point down make an
angle of about 68 degrees with the methylene carbons.
Although slightly different, the other three aromatic rings
that point up all have similar canting angles.
Both of these
compounds show self inclusion in the cavity between the three
'•up" aromatic rings.
The lower rim substituent on the single
alternate aromatic ring interacts in the cavity.
For 2c the
ethyl substituent points into the cavity but does not show
any strong interactions.
Compound 2d shows a similar
interaction with the dinitrobenzoyl substituent.
This
aromatic ring fits further into the cavity than the ethyl on
38
Molecular Geometry of 2c
Molecular geometry of 2d
Figure 11. Molecular geometries for structures 2c and 2d
39
2c and appears to be held by CH - K interactions with the tbutyl substituents.
Of the four crystal structures that are 1,2-dihydroxy,
two crystallise in the "cone" and two crystallise in the
"partial cone" conformation, directed by the up-down
arrangement of the two substituted aromatic rings.
The two
calixarenes in the "cone" conformation both show
intermolecular host guest interactions; the first showing
inclusion of a guest ethanol molecule and the second with
inter-calixarene inclusion.
Both these guests are held by CH
- 7t interactions with the aromatic rings of the calixarene.
The two calixarenes in the "partial cone" conformation have
intramolecular host guest interactions.
In both cases the
lower rim substituent on the single alternate aromatic ring
arranges itself so that it may interact with the cavity.
In
one case the ethyl substituent simply blocks the cavity.
The
other inclusion complex has the dinitrobenzoyl substituent
held within the ring by CH - % interactions with the t-butyl
substituents.
3.5.
1,3-dihydroxycalix[4]arenes
The CCD search found nine crystal structures of
calix[4]arenes that are 1,3-disubstituted on the lower rim.
The general representation of these calixarenes is shown in
Table 13.
All of these 1,3-disubstituted calixarenes are in
40
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t>
i/i in in h in in in in
a)
n
w
a)
a
0)
u
<D
*0
r—i
L-J
cc
X
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td
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4J
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4J 4J
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41
the "cone" conformation which is directed by the presence of
two hydrogen bonds.
The first of these two hydrogen bonds is
between the phenolic oxygen and one of the two adjacent ether
linkages and the second hydrogen bond occurs between the
other phenolic oxygen and the other ether linkage.
Since in
most cases the hydrogen involved in this bond can not be
found on the density map, the only indication of its
existence is a short average oxygen-oxygen distance of 2.81
A.
The average distance between the two oxygens that are not
hydrogen bonded is 2.99 A for all nine crystal structures.
For these nine compounds the observed cavity geometry
does not appear to be affected by the nature of the
substituent on the upper and lower rim but by intermolecular
interactions.
Seven of the nine crystal structures, 3a - f, do not
show the presence of a guest within the cavity or any other
unusual intermolecular interaction in the crystal packing.
Each of these calixarenes crystallises in a "flattened cone"
conformation where two alternate aromatic rings are almost
parallel and the second two make a mutual obtuse angle.
A
diagram of the mean conformation and a list of plane angles
for these seven structures is shown in Table 14.
In all cases the two rings which are almost parallel, A and
C, are substituted on the lower rim.
These lower rim
substituents are directed away from the center of the cavity
42
in a manner that reduces steric interactions.
The other two
apings B and D are unsubstituted and are flattened.
Table 14.
Mean molecular plane angles of structure 3a - £
Plane
A
B
C
D
A - C
B - D
Degrees
78.2
40.3
77.5
39.0
24.3
102.3
This "flattened cone" conformation does not provide a
sufficient cavity to observe host guest interactions.
There are two examples of a neutral guest molecule
interacting in the cavity of a 1,3-dihydroxy calixarene.
In
the crystal structure of 3h there are two inequivalent
structures in each unit cell.
Figure 12 shows a diagram of
both of these structures and thier plane angles are listed in
Table 15.
Table 15.
Molecular plane angles of structure 3h
Plane
A
B
C
D
A - C
B - D
3h (A)
62.6
56.5
62.7
52.4
54.7
57.6
3h (B)
58.1
56.7
60.0
58.3
61.9
71.1
Structurally, 3h has a more open conformation than the
other 1,3-dihydroxy relatives.
The shape of the cavity is
43
Molecular Geometries of 3h
Figure 12.
Molecular geometries for structure 3h
44
more symmetrical and more closely resembles the cavity shape
of tetrahydroxy calixarenes.
It is however less
symmetrically shaped due to the presence of two alkyl
substituents on the lower rim that change the hydrogen
bonding network and introduce steric repulsion between the
two substituents.
The other 1,3-dihydroxy calixarene that has an inclusion
complex is 3i. In addition to the inclusion of a guest, there
is an intermolecular interaction in the crystal packing.
The
diagram of the crystal packing, conformation of the
individual molecule and a list of plane angles is shown in
Figure 13.
The crystal packing shows that there are two
picric acid molecules stacked on the outside of the molecule.
This is the only example of a molecule interacting with the
exterior of the calixarene cavity. Similar to 3h, 3i appears
to open its cavity to accomidate the guest molecule.
The observed conformation of 1,3-dihydroxy calix[4]
arenes is directed by the presence of two alternating
hydrogen bonds and steric repulsion due to the introduction
of an alkyl substituent on two of the positions.
All nine of
these calixarenes are found in a "flattened cone"
conformation.
Although seven of these nine crystal
structures do not have a guest within the cavity, the fact
that two do have host-guest properties indicates that these
calixarenes are capable of host-guest interactions given the
m
proper conditions.
45
Crystal packing of 3i
%
fc..?
fe
'
'
C-C
Molecular geometry and plane angles of 3i
Plane
A
B
C
D
A - C
B - D
Degrees
66.8
52.1
66.8
52.1
46.4
75.8
Figure 13 Crystal packing, molecular geometry and plane
angles for structure 3i
46
3.6.
Monohydroxycalix[4]arenes
There are three crystal structures of calixarenes that
are trisubstituted on the lower rim.
Table 16 shows the
general representation of these three compounds.
The conformation of these compounds is directed by the
manner in which the calixarene is synthesised.
If all three
substituted aromatic rings are syn the solid state
conformation is found as a "cone".
if one of the three
substituted rings is anti the -partial cone" conformation is
found in the solid state.
Two compounds, 4b and 4c are in
the "cone" conformation and 4a is in the "partial coneconformation.
A diagram of the solid state structure of 4b
and 4c are shown in Figure 14. Table 17 shows the plane
angles of the aromatic rings in this conformation.
Table 17.
Molecular plane angles of structure 4b and 4c
B
«.6
C
d
A - o
B - D
81-1
«•?
4 1
-x
4
4B
-7
87.4
90 7
'
11.5
Both of these compounds crystallise in a "pinched coneconformation where two of the alternating rings are almost
parallel and the other two rings are almost normal.
The
three lower rim alkyl substituents arrange themselves so that
47
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O OJ (N
<D rH rH LO
M-J
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(2)
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48
Molecular Geometry of 4b
Molecular Geometry of 4c
Figure 14. Molecular geometries for structures 4b and 4c
49
they point away from the cavity of the calixarene in order
to reduce steric interactions.
The crystal packing of these
two compounds shows no unusual intermolecular interactions
and much like their other "pinched cone" relatives there are
no host guest interactions.
Both 4b and 4c have a single
hydrogen bond occurring between the phenolic oxygen and one
of the adjacent ether oxygens.
Structure 4c has a more symmetrical cavity shape than
4b.
The "parallel" rings in 4c both fold away from the
cavity making an interplanar angle of 11.5 degrees. The other
two aromatic rings, phenol and methyl ether, make an
interplanar angle of 90.7 degrees.
In compound 4b the
"parallel" rings are asymmetric with one ring bent in toward
the cavity at 98.5 degrees and the second ring bent away from
the cavity at 85.2 degrees with respect to the methylene
carbons.
The interplanar angle between these two rings is
-4.1 degrees that indicates that the para positions fold over
to cover the cavity.
The other two aromatic rings, phenol
and methyl pyridine ether, fold out making an interplanar
angle of 103.1 degrees.
Although there are no solid
indications as to the preference for symmetric and asymmetric
conformations, it is probably related to the nature of the
lower rim substituents.
There is one structure, 4a, of a calixarene,
trlsubstitued on the lower rim that is in a "partial cone"
50
conformation. Table 18 shows a diagram of the solid state
structure as well as the plane angles of the aromatic rings.
Table 18.
PXane
A
B
C
D
A - C
B - D
Molecular plane angles of structure 4a
4a
-70.3
70.3
39.3
77.7
70.4
32.0
The phenolic unit and its two adj^enc aromatic rings, which
are substituted with dinitrobenzoyl groups, are pointed down.
The fourth aromatic ring is oriented with the lower rim
substituent pointing up.
The presence of a hydrogen bond
between the phenolic unit and the adjacent ether oxygen,
indicated by the short oxygen-oxygen distance of 2.87 A ,
prevents rotation about the methylene bridge to form a "1,3alternate" conformation.
The crystal packing shows no
unusual intermolecular interactions.
The three "up" rings make angles with the methylene
carbons of 70.3, 39.3 and 77.7 degrees.
This orientation of
these rings forms a cavity that allows a intramolecular hostguest interaction with the lower rim substituent of the
'.'down" aromatic ring. This ring lies at an angle of -70.3
degrees.
The dinitrobenzoyl substituent lies in the cavity
51
if the calixarene held by CH - „ interactions with the parafc-butyl substituents.
The conformation of the monohydroxy calix[4]arenes is
determined by the up-down arrangement of the substituted
aromatic rings. Two of the calixarenes have the substituted
aromatic rings all arranged syn and are found in a "pinched
cone" conformation. The third calixarene has one substituted
aromatic ring anti which produces a "partial cone"
conformation. Neither of the two calixarenes in the "pinched
cone" conformation have host guest interactions which is not
unusual due to the close interactions between the two upright
aromatic rings. The calixarene in the "partial cone"
conformation shows intramolecular host-guest interactions
with the lower rim substituent on the single anti aromatic
ring. The dmitrobenzoyl substituent is held in the cavity
by CH - TC interactions with the upper rim t-butyl
substituents.
CHAPTER 4
SOLID STATE CONFORMATION OF CALIX[4]ARENES
WITHOUT INTRAMOLECULAR HYDROGEN BONDING
4.1.
Introduction
There are 39 crystal structures of calixarenes which do
not show the presence of intramolecular hydrogen bonding
interactions.
These crystal structures may be partitioned
into five different categories that are dependent on the size
of the lower rim substituents, and the conformation in which
the calixarene is synthesised.
When the lower rim
substituents are smaller than ethyl, calixarenes are
conformationally mobile and may be found in any of the four
conformations ("cone", "partial cone", "1,2-alternate", "1,3alternate").
When the lower rim substituents are ethyl or
larger, the conformation of the calixarene may be thought of
as "frozen" with no conformational mobility.
These crystal
structures are categorized into the four conformations
dependent on the manner in which the calixarene was
synthesised.
Although the gross geometry is defined by the
conformation, the "fine" geometry is directed by a series of
complicated inter and intramolecular interactions.
53
4.2.
Tetraalkylated Calix[4]arenes in the
"Cone" Conformation
The CCD search resulted in twenty-one crystal structures
of calix[4]arenes which are tetrasubstituted and frozen in
the -cone" conformation.
Table 19 shows the general
representation of these compounds.
The crystal packing of
these calixarenes show no unusual intermodular
interactions, therefore the conformation of these compounds
is directed by intermolecular effects from both the upper and
lower rim substituents.
Seventeen, 5a - q, of the twenty-one compounds have a
t-butyl substituent in the para position and do not form
host-guest complexes.
All of these crystal structures may
be thought of as -pinched cone" conformations with two of the
aromatic rings being "normal" and the other two rings
essentially "parallel".
There are two subdivisions that are
observed in these compounds due to the orientation of the two
"parallel"
rings. Ten,
5a - h, of the seventeen crystal
structures may be described as symmetric, where the two
parallel rings both fold slightly away from the center of the
cavity.
There are seven structures, 5i - g, that are
asymmetric where one ring folds slightly into the cavity
(angle > 90 degrees) and the other folds slightly away from
the cavity.
The mean angles for these structures are shown
in Table 20 with a descriptive diagram for the sy^etric and
asymmetric crystallization patterns.
54
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Symmetric
Plane
A
B
C
D
A -C
B -D
Degrees
85.9
45.9
85.3
45.3
7.7
88.5
Asymmetric
Plane
A
B
C
D
A -C
B -D
94.2
46.6
82.9
41.9
4.3
90.7
Table 20. Descriptive plane angles for symmetric and
assymetric "cone" conformations
56
For both symmetric and asymmetric structures the lower
rim substituents arrange themselves to reduce steric
interactions, and these appear to have no effect on the
geometry of the cavity.
The lower rim substituents attached
to the "parallel" rings point out away from the cavity, and
the group attached to the "normal" r i a g s
cavity.
point down
^
^
There is no obvious preference for symmetric versus
the assymetric conformations.
There are three calixarenes that have para substitutents
that are sterically smaller than t-butyl, 5r, 5t and 5u.
A
comparison of the crystal structures of 5r and 5q shows that,
without a sterically large para substituent, the two
"parallel" rings fold in over the cavity.
5, has p-t-butyl
and 5r has a p-hydrogen and both calixarenes have the same
lower rim substituents: methyl pyridines.
The crystal
structures of these two compounds are shown in Figure 15.
The plane angles are listed in Table 21.
Table 21.
Molecular plane angles for structures 5q and 5r
Plane.
A
2
£
A - C
B - D
5q
Dearppg
90.0
51
8
5r
Degrees
1n
i
i
-3
26*S
99*7
52.6
o 7
"
77 c
5 6
-
'J
-3
-16.0
113.2
81
44 00
57
Molecular Geometry of 5r
Molecular Geometry of 5q
Fioure 15. Molecular geometries for
structures 5r and 5q
58
In the p-t-butyl calixarene, 5<i, the two "parallel"
rings are arranged in an asymmetric fashion with one ring at
greater than 90 degrees and the other ring bent away from the
center of the cavity. The interplanar angle (8.7 degrees) of
these two rings indicates that the rings fold away from the
center of the cavity, without this sterically large t-butyl
substituent, in 5r, both arc^tic rings fold into the cavity
(interplanar angle of -16.0 degrees) so that the two phenolic
oxygens are bent out.
The conformational characteristics of 5r are also
observed in the two other crystal structures of calixarenes
with para substituents smaller than t-butyl. The mean
geometry of these three compounds 5r, 5t, and 5u is shown in
Table 22.
Table 22. Mean conformation of calixarenes with small para
substituents
Plane
A
B
c
D
Dearppg
100.4
30.9
99.7
37.8
A
~
c
-20.2
B
~
D
111.2
in all four cases the two "parallel" rings fold into the
cavity as observed in 5r. The presence of meta substituents
in Su shows no effect on the preferred conformation. None of
59
these three crystal structures show the presence of a guest
within the cavity.
There is one example of a tetrasubstitued calix[4]arene
that shows host-guest behavior. Table 23 shows the molecular
geometry and plane angles for structure 5s with its 1:1
acetonitrile clathrate.
Table 23.
Molecular plane angles for structure 5s
A
B
D
A
B
~ C
~D
Deareps
65.4
65.4
65.4
65.4
49.2
49.2
Unlike other tetrasubstituted calixaren'es this compound
Shows C 4 v symmetry.
The aromatic rings are all canted at 65.4
degrees with an interplanar angle of 49.2 degrees.
These
canting angles shciw that the calixarene cavity adopts a more
open shape than the other tetrasubstitued calixarenes, and
most closely resembles the shape of the tetrahydroxy
compounds that have an average canting angle of 55.1 degrees
and an interplanar angle of 69.5 degrees.
The interplanar
angle for this tetrasubstituted calixarene is about 20
degrees smaller which can be rationalised by the increase in
stenc repulsion from the presence of lower rim ether
linkages.
60
Twenty of the twenty-one crystal structures that are
tetrasubstituted crystallise in a "pinched coneconformation.
The calixarenes that have para t-butyl
substituents on the upper rim either crystallise with both
"Pinched" rings bent out or one bent in and the other bent
out.
Sterically small para substituents allow the "pinched"
rings fold into the cavity.
There is only one crystal
structure, 5s, that has host guest interactions.
Due to the
small cavity formed in this complex, one may presume that
only sterically small guests, such as acetonitrile, may be
held within the cavity of these calixarenes.
4.3.
Tetraalkylated Calix[4]arenes with Small
Lower Rim Substituents
Unlike the other tetrasubstituted calixarenes that are
synthesised in a single conformation, these calixarenes
posses lower rim substituents which are small enough to
rotate though the cavity.
This rotation allows the
caiixarene to adopt of any of the four standard conformations
("cone", -partial cone-, -1,2-alternate-, and "1,3altemate") .
There are eight crystal structures that are
tetrasubstituted and allow this freedom of rotation.
The
general representation of these compounds is shown in Table
24.
Of these eight crystal structures, seven, 6a - g,
crystallise in a "partial cone- and one, Sh, in the "cone"
conformation.
61
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62
These seven calixarenes that crystallise in the "partial
cone" conformation all have similar geometries. A diagram of
the mean geometry of these compounds and their mean plane
angles are shown in Table 25.
Table 25. Mean conformation for "partial cone" structures
?lane
A
B
£
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D
~
C
"D
Degrees
-90.4
90.6
3
°.6
92.2
8
-
5
59.8
As seen in Table 25, one aromatic ring is pointed down
at -90.4 degrees. The two aromatic rings next to the ring
pointing down make angles of 90.6 and 92.2 degrees with an
interplanar angle of 8.5 degrees that means that these two
planes bend in over the cavity. The fourth aromatic ring
that is alternate to the one facing down lies at a mean angle
of about 30.6 degrees. The crystal packing of these
compounds shows no unusual intermolecular interaction.
The "partial cone" conformation provides a shelf for a
guest to interact with the cavity of the calixarene but
inclusion of a guest molecule is only observed in structure
6d.
m
6d there is a chloroform guest residing in the cavity
of the calixarene that is being held by CH - % interactions.
The lack of guest molecules in the other six structures is
63
due to steric affects from the two alternate aromatic rings
Pinching over the cavity and the lower rim substituent of the
aromatic ring pointing down effectively blocking the cavity.
The steric size of the para substituents appears to have
no effect on the observed conformation of these structures.
Structures 6a and 6b both have t-butyl groups in the para
position and compound 6d has a sterically smaller bromine in
the para position but there is no significant difference in
the conformation of these two compounds.
The crystal structure of p-phenylcalix[4]arene
tetramethyl ether, 6h, crystallises in a -pinched coneconformation.
it has been reported that this compound exists
in the "partial cone" conformation in solution during room
temperature NMR analysis which indicates that there was a
change in conformation during crystallization. Figure 16
shows the conformation of a single molecule, plane angles and
the crystal packing diagram for 6h.
This crystal structure shows that two of the aromatic
rings are bent in over the cavity at an angle of 95.8 degrees
for both rings with an interplanar angle of -11.5.
The ipso
carbons on the para phenyl substituents are 4.2 A apart which
dicative of n - n interactions.
The nature of this k -
K interaction precludes this compound from acting as a host
and no guests are observed in the cavity.
The other two
aromatic rings make an angle of 40.1 degrees with the mean
plane of the methylene carbons.
Tbis cavity is similar to
64
Crystal Packing of 6g
to
Q
Molecular geometry of 6g
Plane
A
B
C
D
A - C
B - D
Figure 16.
Decrrpps
95.8
40.1
95.8
40.1
-11.5
80.3
Crystal packing and molecular geometry for 6g
65
that observed with tetrasubstituted
para s u b s t i t u t e d .
calixarenes
with
snail
Although phenyl would not be classified
as a small substituent, the presence of the n - n
interactions emulate the effect.
Analysis of the crystal
packing of this coirpound (Figure 16) shows the presence of
intermolecular % - * interactions between the p-phenyl rings.
These jt - 7t interactions may account for the preference of
this compound crystallising in the "cone- conformation over
the more commonly observed "partial cone" conformation.
The observed preference for calixarenes with small l o w e r
rim substituents to crystallise in a "partial cone" indicates
that this conformation is the most energetically favorable,
which has been substantiated by molecular orbital
calculations. 52
similar to other calixarenes in the "partial
cone" conformation, these calixarenes provide a cavity for
the inclusion of a guest.
In all but one structure the guest
interaction is precluded by the presence of the lower rim
substituent on the anti ring blocking the cavity,
in the
single structure, 6d, with a guest, the chloroform is held in
the cavity by CH - n interactions.
66
4.4.
Tetraalkylated Calix[4]arenes in the
Partial Cone" Conformation
Four of the compounds, 7a - a, f r o m the CCD search are
frozen in the "partial cone" conformation.
The general
representation of these compounds is shown in Table 26.
Each
of these structures are conformational^ frozen due to large
lower rim substituents. The crystal packing diagrams of these
four structures shows no unusual intermolecular interactions.
These four structures indicate that the only significant
deviation in the geometry of the calixarene is due to
inclusion complexes within the cavity.
The crystal structures of 7a and 7d show no inclusion
7a has acetyl substituents on the lower rim and
properties.
t butyl groups on the upper rim.
The crystal structure of 7d
has methyl pyridine substituents on the lower rim and
hydrogen on the upper rim.
Figure 17 shows the structure of
7a and 7d in the solid state. The plane angles for these two
structures are shown in Table 27.
Table 27.
Molecular plane angles for structure 7a and 7d
£1
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B
c
D
A - c
Degrees
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86 8
39 3
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-86.3
90.7
44.0
88.1
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68
Molecular geometry of 7a
Molecular geometry of 7d
Figure 17. Molecular geometries for structures 7a and 7d
69
Comparison of these two structures with the mean
conformation of the seven "partial cone" structures with
small lower rim substituents shows that there is only a
slight deviation between the two preferred conformations.
The lower rim substituents all arrange themselves so that
they point away from the cavity of the calixarene and
minimize steric interaction.
The crystal structures of 7b and 7c both show inclusion
properties in the cavity.
Figure 18 shows the structure of
7b and 7c in the solid state. The plane angles for these two
structures are shown in Table 28.
Table 28.
Molecular plane angles for structure 7b and 7c
Plane
Degress
R
°
S
A ? C
B
B
Dn
~59*5
72.0
61.9
61 5
46 6
'
2.7
Degrees
-75.3
67.2
53.2
77.2
22.4
35.8
Structure 7c is selectively substituted so that there is
an ethyl ester substituent on rings A and C, and methyl
pyridine groups on rings B and D.
These lower rim
substituents arrange themselves as to reduce steric
interactions and do not appear to have an effect on the
conformation of the calixarene.
There is an acetcnitrile
70
Molecular geometry of 7b
Molecular geometry of 7c
Figure 18. Molecular geometries for structures 7b and 7c
71
guest held within the cavity oriented so that the methyl
group interacts with the aromatic rings of the calixarene.
The presence of this guest in the cavity makes the aromatic
rings fold out.
This folding out was also observed with the
tetrasubstituted 5B that adopts a -cone- conformation with an
acetonitrile guest.
The structure of 7b has methyl pyridine substituents on
the lower rim and t-butyl groups on the upper rim.
This
compound shows self inclusion of the methyl pyridine attached
to ring A that should account for the apparent deformation of
the calixarene geometry.
This inclusion complex is held
together via CH - x interactions between the methyl pyridine
group and the methyls of the t-butyl substituents. Comparison
of this structure with 7d, its de-butylated analog, shows
that the presence of t-butyl substituents is necessary for
this self inclusion interaction
The observed cavity of these four calixarenes appears to
be dependent on the presence of a guest within the cavity.
The calixarenes without guest molecules have a closed
conformation with two of the opposite aromatic rings almost
parallel.
Upon introduction of a guest molecule in the
cavity, these two aromatic rings fold out further to
accommodate its presence.
The comparison of 7b and 7d
implies that the p-t-butyl substituents are necessary for the
formation of a host guest complex with an aromatic guest.
72
4.5.
Tetralkylated Calix[4]arenes in the
"1.2-Alternate" Conformation
One of the crystal structures from the CCD search was
tetralkylated and in the -1,2-alternate- conformation.
Compound 8a was synthesised in the "1,2-alternate»
conformation and is held immobile by ethyl substituents which
are sufficiently large as to prevent freedom of rotation. 19
Figure 19 shows a diagram of the crystal structure, plane
angles and a general representation of the molecule of 8a.
The two adjacent aromatic rings are syn making an angle with
the methylene bridges of 83.8 and 47.8 degrees.
two adjacent aromatic rings are also syn.
The other
These two point
down making a -83.8 and -47.8 degree angle with the methylene
bridges. Analysis of the crystal packing of this compound
shows no intermolecular interaction. There is a cavity
present but no guest is observed due to the ethyl
substitutents which point into the cavity creating a selfinclusion interaction.
There is a second crystal structure of a
tetrasubstituted calixarene in the "1,2-alternate"
conformation that is not included in the CCD.
This
structure, 8b, has four butanoate substituents on the lower
rim and is unfunctionalized on the upper rim. 82 Although
complete data is not available for this structure, the
information that is available indicates that these two
structures share similar conformational properties.
The two
73
General Representation and table of plane angles for
structure 8a
~ r
Plane
A
B
C
D
A - C
B - D
CSffrees.
83 .8
47.8
-83.8
-47.8
48.4
51.3
Molecular geometry of 8a
and raolecularegeomet^PofS8atatl°n' t a b l e ° f P l a n e
angles
'
74
adjacent aromatic rings make angles with the methylene
carbons of 48.5 and 81.0 degrees.
The other two aromatic
rings are pointed down related by a plane of symmetry making
angles of -48.5 and 81.0 degrees.
In this complex, the lower
rim substituents also block the cavity preventing the
formation of an inclusion complex.
Both structures are monoclinic four asymmetric units in
the unit cell. The unit cell for 8a is larger than 8b due to
the presence of para-t-butyl substituents. Both 8a and 8b
show the presence of a cavity that may show host-guest
properties.
Further investigation into the crystallisation
patterns the "1,2-alternate" conformation seems warranted.
4.6.
Tetraalkylated Calix[4]arenes in the
"1,3-Alternate" Conformation
There are five crystal structures from the CCD that are
tetrasubstituted and adopt the "1,3-alternate" conformation.
The general representations of these compounds with the
various substitutents are shown in Table 29.
In the crystal
packing none of these five structures show any unusual
intermolecular interactions.
The cavity shape of calixarenes
in the "1,3-alternate" conformation appears to be dependent
on the steric size of the upper and lower rim substituents.
Compound 9b has sterically small upper and lower rim
substituents. A diagram of the calixarene conformation and
descriptive plane angles is shown below in Table 30. Compound
75
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76
9b is unsubstituted on the upper rim and the lower rim is
tetrasubstituted by an ethyl-ethyl ether substituent.
Table 30.
Plane
A
B
C
D
A - C
B - D
Molecular plane angles for structure 9b
9b
103.7
-104.4
104.3
-102.1
-28.0
-26.5
The lower rim substituents are arranged so that the methylene
carbon points away from the cavity but the substituent itself
shows an interaction within the cavity. Due to the sterically
small nature of these upper and lower rim substituents, the
four aromatic rings of the calixarene fold in over the cavity
effectively covering it.
Structurally the cavity shapes of 9a, 9c, 9d and 9e are
similar. Diagrams of the structures of these four compounds
are shown in Figure 20.
Table 31 lists the descriptive plane
angles for these four structures. All four of these
structures posses substituents on the upper and lower rim
that may be considered sterically large. In each case the
lower rim substituents drape down and fill the void under the
cav
ity.
These substituents do not have any unusual
intramolecular interactions but their steric size appears to
be sufficiently large to alter the shape of the cavity so
77
9a
9c
9d
Figure 20.
9e
Molecular geometries of 9a, 9c, 9d, 9e
78
that the folding in of the aromatic rings as seen in 9b is
not observed.
It is unclear whether the upper rim
Table 31.
and 9e
Molecular plane angles for structure 9a, 9c
Plane
A
B
C
D
A - C
B - D
9a
78.7
-81.5
72.6
-77.0
28.0
21.5
Is
83.0
-87.3
83.0
-87.3
14.0
5.3
M
86.9
79.6
78.6
-73.9
26.6
15.1
'
9d
9e
86.9
-85.7
83 .0
-86.9
9.0
8.3
substituents directly affect the observed conformation but
only in their absence may the aromatic rings fold in over the
cavity.
None of the calixarenes that crystallise in the "1,3alternate" conformation show the ability to have host-guest
interactions.
The arrangement of the aromatic rings so that
the two opposing rings are parallel precludes a guest
formation.
Unlike related "pinched cone" calixarenes which
may distort to accommodate a guest, the calixarenes in the
"1,3-alternate"conformation do not show this flexibility.
The cavity shape of these calixarenes appears to be dependent
on a combination of the steric size of the upper and lower
rim substituents but no conclusions of this sort may be made
given the limited data set.
'
79
4.7. Conclusions
Of the 76 crystal structures of calix[4]arenes analysed
in this survey, fifty-six were "cone", fourteen in the
"partial cone", one in the "1,2-alternate", and five in the
1,3-alternate" conformation. Although the preference for
these four different conformations is determined by their
synthetic design, the molecular recognition properties appear
to be a function of their conformation.
Only compounds that
are found in the "cone" and "partial cone" conformation have
shown inclusion properties. The "1,2-alternate" conformation
shows the presence of a cavity but no host-guest complexes
have been found to date.
The "1,3-alternate" conformation
3oes not appear to be capable of host-guest interaction since
there does not appear to be a cavity present in this
conformation.
Calixarenes in the "cone" conformation most readily
accept guests within its cavity.
calixarenes in
Of the fifty-six
the "cone" conformation, twenty-three
calixarenes show host guest interaction with small organic
guest molecules, or inter-calixarene inclusion complexes.
Although the nature of the upper and lower rim affects the
preferred geometry in the solid state, the shape of
calixarene cavity appears to be dependent on whether or not
the calixarene has a host-guest interaction.
In all cases
where there is a guest present the aromatic rings are folded
80
further out to accommodate for its presence.
?f
a
In the absence
9 u e st the aromatic rings appear to be more closed.
The same host guest relationship is apparent for
calixarenes in the partial cone conformation.
Although
calixarenes in the "partial cone" conformation are apt to
self-inclusion of the lower rim substituent from the single
anti aromatic ring, inclusion of small organic molecules is
also observed.
In cases where there is a guest present in
the cavity, the three aromatic rings fold out to accommodate
its presence.
Alternately, without a guest present the three
aromatic rings are more closed.
All guests present in these seventy-six crystal
structures are held in place by CH-Tt interactions between the
guests and the aromatic rings of the calixarene.
In the
cases where the guest has n orbitals and the host has alkyl
substituents on the upper rim, interaction between the
calixarene alkyls substitutents and the n orbitals of the
guest are also observed.
There are indications that all calixarenes in the "cone"
and "partial cone" conformations are capable of host guest
interaction.
The fact that in all cases where there is a
guest present, the cavity opens up to accommodate the guest
indicates that other host-guest complexes may be observed
given proper crystallisation conditions.
CHAPTER 5
CRYSTAL STRUCTURES OF NEW CALIX[4]ARENES
5.1. Introduction
The solid state structures of four new calixarene
compounds have been determined.
The generic diagrams of
these four compounds are shown in Figure 21.
Figure 21.
General representation of structures I, II,
III, IV.
NHCOCH.
OTos
OH
Structure I
OTos
Structure II
OTos
Obz
Structure III
OTos
Structure IV
82
There are two 1,3-dihydroxycalixarenes that adopt the "cone"
conformation(X and II), one tetrasubstituted "cone" (III),
and one calixarene in the "1,3-alternate" conformation (IV).
four of these compounds were synthesised by Dusan Hesek
in Paul Beer's research group at Oxford University.
Specifically these compounds are intermediates in the
synthesis of calix[4]arene derivatives for use in anion
extraction from aqueous media.
5.2.
Structure I
Crystals of. compound I were obtained from a saturated
solution in chloroform.
The solution was in a sealed
container that was placed in a water bath with a temperature
of 65 C.
Over a period of two months the bath temperature
was lowered to room temperature and clear colorless crystals
with block morphology were obtained.
Due to the solvent
dependent nature of these crystals they were analysed at -60
°C mounted on a glass fiber and held in position with
Paratone-N. Data collection was carried out as described in
the experimental section.
After collection of the diffraction data, the structure
was solved with the use of SHELXS-86.
Information regarding
the collection and processing for structure I is shown in
Table 32. The crystals were found to be monoclinic and in the
space group P2i/c.
There are four calixarenes in the unit
83
Table 32 - X-Ray Crystallographic Collection and Processing
Data for Structure I
,^pirf.iire I
Crystal System
Space Group
Monoclinic
P2i/c
Cell Constants
a,
A
29.373 (2)
b, A
9.647 (1)
c, A
18.328 (2)
b
106.428 (8)
V, A3
mol formula
fw
4981.4 (7)
C48H44CI6N2O10S2
1085.74
4
formular units per cell (Z)
1.448
r, g cm-3
total data collected
6340
independent data I>3 s(I)
3000
R
Rw
GOF
weights
0.0491
0.0498
0.94
[0.04 F 2 + (s F) 2 ]" 1
84
cell with two molecules of chloroform per calixarene.
disorder was found within the lattice.
No
All atoms with the
exception of the carbons of the calixarene framework were
refined with anisotropic thermal parameters.
The hydrogens
attached to the phenolic oxygens were found from an electron
density difference map and all other hydrogen atoms were
calculated in most probable positions.
This refinement
resulted in a final R value of 0.0491.
The structure of the individual molecule is shown in
Figures 22 and 23.
Information regarding the bond lengths,
bond angles, and torsion angles associated with structure I
may be found in Appendix B.
Comparison of these bond lengths
and angles with other 1,3-dihydroxycalix[4]arene show no
unusual deviations.
This calixarene is another example of a
1,3-dihydroxycalix[4]arene which crystallises in a "flattened
cone" conformation where two of the aromatic rings are almost
parallel and the other two form an obtuse angle.
The
preference for the "cone" conformation is directed by the
presence of two hydrogen bonds between the two phenolic
oxygens.
The hydrogens on the two phenolic oxygens were
located from the difference map.
The hydrogen bonds occur
between Olb - Olc and Old - Ola which is reflected by their
short oxygen-oxygen distances of 2.88 and 2.94 A
respectively.
The distances between the two non-hydrogen
bonded oxygens is 3.21 for Ola - Olb and 3.13 for Olc - Old.
Although these differences in oxygen-oxygen distances are not
85
04 Id
C41b
08al
Figure 22 ORTEP diagram of structure I
with thermal
ellipsoids drawn at 50% probability level.
omitted for clarity, (side view)
H atoms are
86
C42d
041d|
C12c
ClOc
ClOa
Cl2a
C41b
CISa
C42b
figure 23 ORTEP diagram of structure I with thermal
ellipsoids drawn at 50 % probability level.
omitted for clarity, (top view)
H atoms are
87
very large, they do indicate that two of the distances are
due to stronger interactions.
These oxygen-oxygen distances
correspond well with other l,3-dihydroxycalix[4]arenes.
The cavity shape of I is defined by the angles between
each of the four aromatic rings and the mean plane of the
methylene carbons as well as the interplanar angle between
the two opposite aromatic rings.
The relevant angles of the
aromatic rings of structure I and the mean values for other
1,3-dihydroxycalix[4]arenes are shown in Table 33.
Table 33. Molecular plane angles of structure I and mean
plane angles for similar 1,3-dihydroxycalix[4]arenes
Plane
a
b
c
d
a - c
b - d
Structure I
80.3 (2)
42.1 (2)
81.2 (2)
40.1 (2)
19.4 (3)
97.8 (2)
mean
78.2
40.3
77.5
39.0
24.3
102.3
The plane angles of the calixarene cavity are verysimilar to the mean plane angles of other 1,3-dihyrdroxy
calix[4]arenes.
The two "parallel" aromatic rings make an
interplanar angle of 19.41(3) (24.3 mean value) degrees and
the two "flattened" rings make an interplanar angle of
97.84(2) degrees (102.3 mean value).
The two tosylate
substituents on the lower rim point away from the cavity. As
seen in Figure 23 (the top view of the calixarene molecule),
88
the tosylates appear to twist around in a counter clockwise
direction.
The crystal packing of I is directed by series of
intermolecular hydrogen bonds and 7U-stacking between adjacent
calixarene molecules.
Figure 24 shows a projection of the
crystal packing looking down the C axis.
The calixarenes are
oriented so that they are in an "up-down" arrangement with
the aromatic ring b stacking on top of aromatic ring d of an
adjacent calixarene( x,y,z) -> {x,3/2-y,z-1/2).
The atoms in
these two rings show close interactions ranging between 3.34
to 3.57 A .
A strong hydrogen bonding interaction occurs
between N4b and 041d related by the transformation of (x,y,z)
-> (x,5/2-y,z+1/2).
The "up-down" relationship of these calixarenes in the
crystal packing creates long threads of molecular calixarenes
which extend the length of the crystal.
Figure 25 shows a
diagram of the unit cell projected down the b axis.
There
are four calixarenes and eight molecules of chloroform in the
cell.
This packing diagram shows a series of layers.
The
top layer has two chloroform molecules followed by two
calixarenes in the next layer, then another layer of
chloroform.
This layering effect of calixarene: solvent:
calixarene is very common to the crystal packing of
calixarenes in general.
These unique clathrate interactions
were first observed by Atwood in a series of papers regarding
the the crystal structures of a series of calix[4]arene
89
Figure 24 A diagram of the crystal packing of structure I
90
y
> - o
Figure 25 A diagram of the unit cell of structure I
91
sulfonate salts where the calixarenes form layers which are
separated by a sheet of water molecules.^6
This layering
affect may also be seen looking down the a-axis.
5.3.
Structure II
Crystals of compound II were grown from a saturated
solution in THF by slow evaporation of the mother liquor at
10 °C.
Clear colorless crystals were obtained.
These
crystals were solvent dependent, quickly decomposing when
left in the open air.
The crystals were mounted in a
capillary tube with the addition of a small amount of mother
liquor prior to sealing the capillary.
Data were collected
as described in the experimental section.
After collection of the diffraction data, the structure
was solved using SHELXS-86.
The crystals were found to be
monoclinic in the P2±/n space group.
Information regarding
the collection and processing of the data for structure II is
given in Table 34. There are four calixarene molecules in the
unit cell with 2 molecules of THF per calixarene.
The
solvent molecules in the lattice were disordered and their
absolute positions were difficult to identify.
Hydrogen
atoms were generated and also found on the difference map.
The hetero atoms and methyl groups were turned anisotropic
prior to the final refinement which resulted in an R value of
0.0698.
92
Table 34 - X-Ray Crystallographic Collection and Processing
Data for Structure IX
St-Turture XX
Crystal System
Space Group
Monoclinic
P2i/n
Cell Constants
a, A
11.7184 (8)
I
I
b, A
c, A
b
V, A3
mol formula
15.023 (1)
27.687 (3)
99.333(7)
4809.6 (7)
C50H56N2O14S2
967.09
fw
4
formular units per cell (Z)
1.335
r, g cm-3
6159
total data collected
2994
Independent data I>3 s(I)
0.0698
R
0.0701
Rw
GOF
wieghts
1.39
[0.04 F 2 + (s F) 2 ]" 1
93
The structure of the individual calixarene molecule
resembles other 1,3-dihydroxycalix[4]arenes. Tables of bond
lengths, bond angles, and torsion angles are shown in
Appendix C. These distances and angles correlate well with
other 1,3-dihydroxycalix[4]arenes. Figure 26 shows the
geometry of a single calixarene molecule in this structure.
Table 35 shows the relevant plane angles of structure II and
the mean values for other 1,3-dihydroxycalix[4]arenes.
p
Molecular plane angles of structure II and mean
ne angles for similar 1,3-dihydroxycalix[4]arenes
Plane
_
Structure TT
—
81.2 (2)
o
d
d
£ ~ d2
b
"
ll'l (3)
(2)
32.2 (4)
20 1
• (6)
"6-0 (3)
mean
78-2
40.3
- 5o
39
243
102[3
77
The plane angles of the two parallel rings are slightly
deviated from the mean conformation of other 1,3-dihydroxycalix[4]arenes. The two "flattened" rings are bent out
further making an angle of 116.0(3) degree angle compared to
the mean value of 102.3 degrees usually observed for these
calixarenes. The other two "upright" rings are reasonably
similar to the mean.
This deviation in the plane angles of the two
"flattened" rings is due to an intermolecular hydrogen
bonding interaction of the phenolic oxygens with one of the
94
04al
08al
08a2
ClOa
CIS a
Figure 26 ORTEP diagram of structure IX with thermal
ellipsoids drawn at 50 % probability level.
omitted for clarity.
H atoms are
95
THF molecules.
The normal arrangement of the hydrogen
bonding network which involves two hydrogen bonds between the
phenolic oxygens and the oxygens of the ether linkages is not
present in this structure.
In structure II there is one
intramolecular hydrogen bond which occurs across the bottom
of the cavity between
Old to 01b (2.91 A). The second
phenolic oxygen, 01b, has an intermolecular hydrogen bond to
oxygen of a THF molecule which resides under the cavity of
the calixarene with an oxygen-oxygen distance of 2.77 A as
shown in Figure 27.
This is the only example of a 1,3-
dihydroxycalix[4]arene which prefers an intermolecular over
an intramolecular hydrogen bond. Due to the presence of this
intramolecular hydrogen bond across the cavity, the two
phenolic rings may fold further into the ring, as demostrated
by the increased dihedral angle between planes b and d.
The two lower rim tosylate substituents arrange
themselves under the cavity as to minimize steric
interactions.
The presence of the THF under the cavity
appears to have no significant affect on the arrangement of
these substituents.
One of the tosylates is directed so that
it points down and the other tosylate sticks out away from
the cavity.
The crystal packing in the unit cell is shown in Figure
28.
The unit cell contains four calixarene molecules and
eight molecules of THF.
Although the packing arrangement of
the individual calixarene molecules is different from that
96
04 al
04cl
08al
08a2
ClOa
C15a
Figure 27 ORTEP diagram of structure IX with thermal
ellipsoids drawn at 50 % probability level.
omitted for clarity.
H atoms are
Hydrogen bonding interaction between
the 01b and the THF molecule.
97
\
3*T
2
Figure 28 A diagram of the unit cell for structure II
98
observed m
Observed.
structure X, the same layering effect is
The layers of clathrate guest molecules and
calixarenes alternate along the c and a axis.
Similar to
Structure X, the calixarenes are lined in long threads which
extend the full length of the crystal.
Although one of the
solvent molecules is held in position by a strong hydrogen
bond, the second THF is held in place by weak Van der Walls
forces in a cavity formed between the calixarenes.
This
second molecule of THF which is weakly held in position is
presumably responsible for the solvent dependent nature of
these crystals.
The nitro substituent on the para position is twisted
slightly out of plane with the aromatic ring by four degrees.
This twisting is due to a strong intercalixarene interaction
between 04al and C7b (3.27 A ) .
These two calixarenes are
related by the transformation (x,y,z) to (3/2-x, y-1/2, 1/2z).
The oxygen of the nitro substituent appears to have an
interaction with one or both of the methylene hydrogens.
5.4.
Structure III
The compound in structure III is tetrasubstituted and
adopts the "cone" conformation.
The lower rim substituents
are large enough to prevent conformational mobility.
Crystals of structure III were grown from a saturated
solution of THF at 10 °C over a period of two months.
Clear
colorless crystals in the shape of long blocks were obtained.
99
These crystals were found to be solvent dependent and were
mounted with mother liquor in the capillary prior to sealing.
Data collection proceeded as outlined in the experimental
section.
The crystals were found to be orthorhombic and in the
space group C222i.
Specific information on the collection
and processing of this structure is shown in Table 36. The
structure was solved using SHELXS-86 where four calixarenes
and twelve THF molecules were found in the unit cell. The
solvent molecules in the lattice showed a significant amount
of disorder which was treated by fixing the bond lengths and
angles for these molecules prior to final refinement. All non
hydrogen atoms were treated with isotropic thermal parameters
and the positions of the hydrogen atoms were calculated in
most probable positions prior to the last refinement which
resulted in an R value of 0.065.
The molecular structure of III, Figure 29, is in a
"pinched cone" conformation in which two aromatic rings with
lower rim benzyl substituents lie flattened and the two rings
with lower rxm tosylate substituents are pinched in over the
cavity of the calixarene.
miror plane.
The molecule lies on a two fold
Specific information regarding bond lengths and
angles for structure may be found in Appendix D. The
conformational characteristics of this structure match well
with other tetrasubstitueted calixarene in the "cone"
conformation without sterically bulky para substituents.
100
Table 36 - X-Ray Crystallographic Collection and Processing
Data for Structure III
Structure TTT
Crystal System
Space Group
Orthrombic
C222i
Cell Constants
a, A
19.044 (2)
b, A
21.522 (2)
c, A
15.362 (1)
V, A3
mol formula
fw
formular units per cell (Z)
6296 (1)
C68H70N2O15S2
1219.45
4
r, g cm-3
1.286
total data collected
2143
Independent data I>3 s(I)
1074
R
0.0565
Rw
0.0742
GOF
1.07
*
weights
[0.04 F 2 + (s F)2]-l
101
04a
Clla
ClOb
Cllb
Figure 29 ORTEP diagram of structure III with thermal
ellipsoids drawn at 50 % probability level.
omitted for clarity.
H atoms are
102
Table 37 shows the planes of the aromatic rings for Structure
XXI and also the mean value of similar structures.
Table 37. Molecular plane angles of structure tit =nri
d
Plane angles for similar calix[4]arenes
^
Plane
Mear
B
C
D
A-C
B - D
^
1
?2'q
qq-?
!??*?
on"?
~20-1
3
7
-
Structure ITT
6
(3)
102.36(8)
37.59(8)
102.1(3)
104 8
- (2)
-24.5 (4)
The two flattened rings are canted at angles of about 37
degrees with an interplanar angle of 104.8(2) degrees.
The
two parallel aromatic rings fold over the center of the
cavity with an interplanar angle of -24.5(4) degrees.
These
angles are very similar to the mean values for calixarenes of
this type.
The methylene carbon attached to the phenolic
oxygens point away from the cavity and their substituents
arrange themselves under the cavity to reduce steric
interactions.
The arrangement of the lower rim substituents shows no
unusual characteristics.
The two benzyl groups are attached
to the rings which are folded out at an obtuse angle and the
two tosylate substituents are attached to the rings which are
pinched over the cavity.
The two benzyl substituents occupy
the area under the cavity with one bent to the right and the
other bent to the left.
If one were to look at a top view of
103
this structure, the tosylates would both be pointed out from
the underside of the cavity and would appear to twist in a
clockwise direction similar to their arrangement in structure
I.
The crystal packing diagram of the unit cell, Figure 30,
shows four calixarene molecules and twelve THF molecules.
The calixarene molecules in the crystal lattice may be
thought of as occupying octahedral positions and there are
two THF molecules in the tetrahedral holes in the lattice.
There are several close contacts between each calixarene with
other calixarene and the solvent molecules but none appear to
have a significant effect on the observed geometry of the
calixarene molecule.
5.5. Structure IV
Compound IV was synthesised in the "1,3-alternate"
conformation where both of the lower rim substituents are
large enough to prevent rotation about the methylene bridges.
Crystals of IV were grown by slow evaporation of a saturated
THF solution at room temperature.
The clear colorless
crystals with a block morphology were mounted in a capillary
and held in place using silicon grease.
The data collection
proceeded as outlined in the experimental section.
The structure was solved using SHELXS-86.
Specific
information regarding the collection and processing of the
data for structure IV is shown in Table 38.
The crystals
104
ft
^
i,^
w
yv
^
w
Figure 30 A diagram of the unit cell for Structure III
105
Table 38 - X-Ray Crystallographic Collection and Processing
Data for Structure
VI
Strunt-m-P ty
Crystal System
Space Group
Monoclinic
C2/c
Cell Constants
V, A
a, A
22.835 (3)
b, A
15.885 (1)
c, A
15.582 (2)
b
117.067 (9)
3
mol formula
fw
formular units per cell (Z)
r, g cm-3
5033.1 (9)
C56H46N2O12S2
1003.13
4
1.324
total data collected
3225
Independent data I>3 s(I)
1601
R
0.0567
Rw
0.0548
GOF
wieghts
1.34
[0.04 F 2 + (s F) 2 ]— 1
106
were found to be monoclinic and in the space group C2/c.
Four calixarenes occupied the unit cell and no disorder was
found m
the lattice.
Hydrogen atoms were found on the
difference map as well as being assigned positions.
All
sulfurs, oxygens, nitrogens, and methyls were turned
anisotropic which resulted in a final R value of 0.0567.
The molecular structure of IV, shown in Figure 31, is in
the "1,3-alternate" conformation in which two alternate
aromatic rings are pointed up and the other two rings are
pointed down.
The calixarene lies on a crystallographic two
fold rotational axis.
Table 39 shows the angles of the
planes with the methylene carbons and the interplanar angle
between the two alternate planes.
Table 39. Molecular plane angles of structure XV
Planes
£
f,
J,
A - A~
B
" B'
Degrees
87.6
-87.2
87.76
"87-29
4.6
5.5
(2)
(2)
(7)
(5)
(4)
(5)
Each of the four aromatic rings make an angle of about
87 degrees with the methylene carbon plane.
The resulting
angle between alternate aromatic rings is about 5 degrees.
The shape of this cavity is very similar to other "1,3alternate" crystal structures which have large lower rim
107
0
ClOa
08 a
C14b
ClOb
Figure 31 ORTEP diagram of structure XV with thermal
ellipsoids drawn at 50 % probability level. H atoms are
omitted for clarity.
108
substituents.
The methylene carbons of the lower rim
substituents point away from the cavity and the substituents
themselves drape down filling the void under the cavity.
The
cavity geometry in this structure most closely resembles
structure 9a. 9a has three sterically large substituents on
the lower rim.
The addition of the fourth sterically large
substituent on the lower rim in IV may account for the
decreased interplanar angle between planes A and C.
The
close interaction between these aromatic planes does not
provide a cavity for host-guest interactions.
Due to the
strained nature of the "1,3-alternate" conformation, it is
unlikely that these rings may fold open to accommodate a
guest as observed in calixarenes in the "cone" and "partial
cone" conformations.
The crystal packing which is shown in Figure 32 shows
that these calixarenes arrange themselves in layers.
The
layer shown at the top of the diagram has two calixarenes
oriented so that the benzyl substituents on both calixarenes
are interacting in the center and the tosylate substituents
are on the exterior.
The second layer down has the alternate
arrangements with the tosylates in the center and the benzyl
groups point out.
These layers alternate along the C axis of
the unit cell forming a series of long threads in the
crystal.
The projection down the A axis, as seen in Figure
33, shows an top view of these "molecular threads".
The
close packing arrangement of these threads provides very few
109
Figure 32 A diagram of the unit cell for structure IV
110
Ficpxre 33 A diagram of the unit cell for- structure XV
Ill
voids in the lattice that would usually be occupied by
lattice solvent.
5.6.
Conclusions
Of the four new crystal structures of calix[4]arenes,
two are examples of calixarenes where the preferred
conformation is determined by intramolecular hydrogen
bonding.
The conformation of the other two calixarene
structures is determined by the manner in which they are
synthesised.
Structure X is a typical example of a 1,3-dihydroxycalix[4]arenes.
This calixarene is found in the "cone"
conformation which is directed by two intramolecular hydrogen
bonds between the two phenolic oxygens and the adjacent ether
linkages.
Structurally this compound has no unusual
characteristics;
the cavity shape and size is very similar
to the mean conformation of calixarenes of this type.
One of
the unique characteristics of this structure is the presence
of intermolecular 7t-stacking and hydrogen bonding
interactions observed in the crystal packing.
The presence
of these intermolecular interactions appears to have no
effect on the preferred conformation of the individual
molecule.
The calixarenes arrange themselves in long threads
which extend the length of the crystal.
Each of these
threads is separated by clathrate solvent molecules.
112
Structure II is an atypical example of a 1,3-dihydroxycalix[4]arene.
The calixarene is in the "cone" conformation
which is directed by the presence of a single intramolecular
hydrogen bond which occurs transannularly between the two
phenolic oxygens.
There is also a second hydrogen bond
occurring between the second phenolic oxygen and a single THF
molecule.
This is the only example of a 1,3-
dihydroxycalix[4]arene which prefers an intermolecular
hydrogen bond over an intramolecular hydrogen bond.
The
presence of this single tranannular intramolecular hydrogen
bond allows the two phenolic oxygens to fold further into the
cavity making the two aromatic rings more flattened.
The
calixarene molecules are arranged in threads separated by
solvent molecules similar to structure I.
Structure III is a typical example of a tetralkylated
calix[4]arene in the "cone" conformation with small para
substituents.
This calixarene is tetrasubstituted with
sterically large lower rim substituents which prevent
conformational interconversion.
The cavity shape and size is
typical for these calixarenes; two of the aromatic rings are
pinched, folding over the cavity and the other two aromatic
rings are folded out with an interplanar angle of about 90
degrees.
The calixarenes are found in octahedral positions
in the crystal packing with two solvent molecules found in
the tetrahedral holes.
113
Structure IV is a typical example of a calix[4]arene in
the "1,3-alternate" conformation.
The lower rim substituents
are sterically large which prevents conformational
interconversion.
Both of the two alternate aromatic rings
have an interplanar angle of about five degrees which is
common for calixarenes in the "1,3-alternate" conformation.
The calixarenes arrange themselves in a head to tail fashion
forming long threads.
The close packing arrangement of these
compounds prevents the presence of clathrate solvent in the
lattice.
None of these four calixarene crystal structures show
the presence of host guest interactions.
After examining
structural characteristics of calix[4]arenes, the absence of
intracavity host guest interactions is not particularly
surprising.
There are no examples of host guest interactions
with compounds similar to structures III and IV.
There are
two examples of 1,3-dihydroxycalix[4]arenes, similar to
structure I and II, which have inclusion complexes but there
are no examples of THF inclusion complexes in any of these
structures.
Further research will be necessary to determine
the chemical characteristics necessary for host guest
interactions.
APPENDIX
A
CDS SEARCH RESULTS
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APPENDIX
B
BOND LENGTHS, BOND ANGLES,
AND TORSION ANGLES FOR
STRUCTURE I
124
Atom 1
Atom 2
S8a
S8a
S8a
S8a
S8c
Ola
08al
08a2
C9a
Olc
S8c
08c 1
S8c
S8c
08c2
C9c
Distance A Atom 1
(e.s.d.)
1.614(5)
Clc
1.427(6)
Clc
1.416(7)
Cld
1.735(8)
Cld
1.621(6)
C2a
1.425(6)
C2a
1.402(6)
C2b
1.751(8)
C2b
Ola
Clb
1.410(9)
Olb
Clb
01c
Clc
1.386(9)
1.412(9)
Olc
04al
Clc
N4a
04a2
Atom 2
C2d
C6d
C3a
Distance A
(e.s.d.)
1.39(1)
1.39(1)
1.39(1)
1.40(1)
1.39(1)
C7a
1.52(1)
C2c
C3b
C7b
C3c
1.39(1)
1.51(1)
1.36(1)
C2c
Clc
1.51(1)
C2d
C3d
1.39(1)
C7d
C4a
1.51(1)
N4a
1.22(1)
1.21(1)
C2d
C3a
C3b
04c 1
N4c
1.21(1)
C3c
C4b
C4c
1.37(1)
04c2
N4a
N4c
C4a
1.23(1)
1.47(1)
C3d
C4a
C4d
C5a
1.37(1)
1.37(1)
N4C
Cla
Cla
C4c
C2a
1.47(1)
1.40(1)
C4b
C4c
C5b
C5c
1.37(1)
1.37(1)
C6a
1.39(1)
C4d
C5d
1.37(1)
Clb
C2b
C5a
C6a
1.39(1)
,Clb
C5c
Cb6
1.38(1)
1.39(1)
C5b
C6b
1.39(1)
C6c
1.38(1)
C12a
C15a
1.54(2)
C6d
C7a
1.38(1)
C12c
C12c
C13c
C13a
01s
01s
C13c
C15c
C14c
C14a
C2s
C5s
1.38(1)
1.52(1)
1.38(1)
1.38(2)
1.46(2)
1.61(3)
C5d
C6a
C6b
C6c
C6d
C9a
C7b
Clc
C7d
ClOa
1.37(1)
1.51(1)
1.53(1)
1.52(1)
1.50(1)
1.37(1)
C2c
C6c
1.38(1)
1.39(1)
125
Atom 1
Atom 2
C9a
C9c
C14a
ClOc
C14c
Bond Distances for Structure I (cont)
Atom 2
Distance A Atom 1
(e.s.d.)
C3s
C2s
1.37(1)
C4s
C3s
1.36(1)
Distance A
(e.s.d.)
1.50(3)
1.46(5)
06s
C7s
ClOs
1.29(4)
1.42(2)
1.40(2)
1.37(2)
C7s
C8s
1.48(3)
C8s
C9s
C9s
1.50(3)
1.44(3)
H3a
1.38(1)
1.29(2)
0.95
C3b
H3b
C3c
Clla
Cllc
1.39(1)
1.44(2)
1.38(1)
C4s
06s
Clla
C12a
Cllc
cm
C12c
C13a
C3a
C9c
ClOa
ClOc
C5s
C13c
ClOs
H13c
0.95
0.95
C13a
H13a
0.95
H3c
0.95
C14a
H14a
0.95
C3d
H3d
0.95
C14c
H14c
0.95
C4b
H4b
C4d
H4d
H5a
0.95
0.95
C15a
C15a
H15al
H15a2
0.95
0.95
0.95
C15a
H15a3
0.95
C5a
C5b
C5c
H5b
0.95
C15c
H15cl
0.95
H5c
0.95
H15c2
C5d
C7a
H5d
H7al
H7a2
0.95
0.95
C15c
C15c
C2s
0.95
C2s
H2sl
H2s2
0.95
0.95
0.95
H7bl
H7b2
0.95
C3s
0.95
C7c
H7cl
H7c2
C7d
C7d
ClOa
ClOc
Clla
H7dl
H7d2
HlOa
HlOc
Hlla
0.95
0.95
0.95
0.95
0.95
C7a
C7b
C7b
C7c
H15c3
0.95
0.95
C3s
H3sl
H3s2
0.95
C4s
H4sl
0.95
0.95
C4s
C5s
C5s
C7s
C7s
C8s
H4s2
0.95
0.95
0.95
0.95
0.95
0.95
H5sl
H5s2
H7sl
H7s2
H8sl
0.95
126
Atom 1
Atom 2
Cllc
C9s
C9s
Hllc
H9sl
H9s2
Bond Distances for Structure I (cont)
Distance A Atom 1
Atom 2
(e.s.d.)
0.95
C8s
H8s2
0.95
ClOs
HlOsl
0.95
ClOs
H10s2
Atom 1
Atom 2
Ola
S8a
Bond Angles for Structure I
Atom 3 Angle
Atom 1 Atom 2
08a
107.2(3) C2a
Cla
Ola
Ola
08a
08a
S8a
08a
S8a
S8a
C9a
08a
S8a
C9a
08a
S8a
C9a
Olc
S8c
08c
Olc
S8c
08c
Olc
08c
S8c
C9c
S8c
08c
08c
S8c
C9c
08c
S8c
C9c
S8a
S8c
Ola
Olc
04a
N4a
Cla
Clc
04a
04a
04a
N4a
C4a
N4a
C4a
N4c
119.0(7) C3c
117.7(7) Cld
117.7(5) Cld
118.9(7) C3d
04c
04c
04c
Ola
N4c
N4c
Cla
04c
C4c
C4c
C2a
Ola
Cla
C6a
Distance A
0.95
0.95
0.95
Atom 3
Angle
C6a
123.4(7)
C2b
117.9(6)
C6b
C6b
C2c
119.9(7)
122.1(7)
109.0(3) 01b
98.8(3) 01b
118.3(4) C2b
111.4(4) Olc
Clc
110.2(4) Olc
108.1(3) C2c
Clc
Clc
C6c
117.1(7)
118.8(7)
C6c
124.1(7)
101.9(3) Old
106.7(4) Old
Cld
C2d
119.2(7)
Cld
C6d
119.7(7)
120.9(4) C2d
107.8(4) Cla
Cld
C2a
C6d
C3a
121.1(7)
110.4(4) Cla
115.0(4) C3a
119.7(5) Clb
C2a
C7d
123.4(7)
C2a
119.4(7)
C2b
C7d
C3b
C2b
C7a
117.9(7)
121.5(7)
C2b
Cla
120.5(7)
C2c
C3c
117.5(7)
C2c
C2c
C2d
C2d
C7b
C7b
C3d
C7c
122.2(6)
120.1(7)
118.8(7)
119.1(7)
C2d
C7c
121.8(7)
124.0(8) Clb
118.5(8) C3b
117.5(7) Clc
123.3(7) Clc
Clb
Clb
Clb
117.2(7)
127
Atom 1
C2a
C2b
C2c
C2d
N4a
N4a
C3a
C3b
N4c
Atom 2
C3a
C3b
C3c
C3d
C4a
C4a
C4a
C4b
Bond Angles for Structure I (cont.)
Atom 3 Angle
Atom 1 Atom 2
C6c
C4a
119.5(8) Clc
C6c
C4b
120.8(8) Clc
C6c
C4c
119.4(7) C5c
C6d
120.4(8) Cld
C4d
C6d
C3a
118.8(8) Cld
C6d
C5a
118.8(7) C5d
C7a
C5a
122.4(8) C2b
C7b
C5b
120.5(8) C2c
Atom 3
C5c
C5d
C7d
Angle
116.2(7)
123.0(6)
120.7(7)
118.0(7)
119.6(7)
C7d
C6a
C6b
122.3(7)
113.1(6)
112.4(7)
Clc
Clc
119.2(7) C2d
118.7(7) C2a
122.1(7) S8a
C7c
C6c
113.7(7)
C7d
C9a
C6d
111.3(6)
119.0(7)
120.0(9) S8a
120.0(8) ClOa
120.4(7) S8c
C9a
ClOa
CI 4a
C9a
C14a
C9c
120.2(8) S8c
121.7(8) ClOc
117.1(7) C9a
C9c
ClOc
C14c
118.7(6)
C9c
C14c
121.4(8)
ClOa
ClOc
116(1)
119.5(8)
C7a
122.6(7) C9c
120.2(7) ClOa
C6b
C5b
118.2(7) ClOc
Clla
Cllc
Clla
Cllc
C12a
Clb
C5b
C13a
C6b
C6b
C12a
C7b
C7b
C15a
121.3(7) CI la
120.5(7) Clla
Ols
124(1)
C12a
C12a
C2s
C13a
C15a
C3s
98(1
Cllc
C12c
C13c
118.8(9) C2s
C3s
C4s
93(2
Cllc
C14c
C12c
C12c
C15c
C15c
120.5(8) C3s
C4s
104(3
C5s
91(2
C12c
C13c
C14c
120.6(9) Ols
121.8(9) C7s
C5s
C4s
C6s
ClOs
105(1
C3c
N4c
C4c
C4c
C3c
C4c
C5c
C3d
C4a
C4d
C5d
C5a
C6a
C4b
C4c
C5b
C5c
C6b
C6c
C4d
C5d
C6a
C6d
C6a
C7a
C6a
Clb
Cla
Cla
C5a
C5c
C5a
CI 2c
119.4(7)
121.5(9)
119.6(7)
120(1)
120.6(8)
120(1)
116(1)
128
Atom 1
C2a
C9a
Atom 2
C13a
C14a
C9c
C2s
C2a
C14c
Ols
C3a
Bond Angles for Structure I (cont.)
Atom 3 Angle
Atom 1 Atom 2
C14a
06s
123(1)
C7s
C13a
118.7(9) C7s
C8s
C13c
117.6(8) C8s
C9s
C5s
06s
107(1)
ClOs
H3a
120
C6a
C7a
C4a
C3a
H3a
120
C6a
C7a
H7a2
109
C2b
C4b
C3b
C3b
H3b
H3b
120
C7a
H7a2
120
H7al
C2c
C7b
H7bl
110
109
C2c
C3c
H3c
120
C2c
C7b
H7b2
109
C4c
C3c
H3c
C6b
C2d
C4d
C3d
H3d
C3b
C5b
H3d
H4b
H4b
C6b
H7bl
C7b
C7b
C3d
C4b
C4b
120
120
120
120
120
C2d
C2d
C7b
C7c
C7c
H7bl
H7b2
H7b2
H7cl
H7c2
109
109
110
108
C3d
C4d
H4d
120
C6c
C7c
C5d
C4a
H4d
H5a
H5a
120
C6c
C6a
C4d
C5a
C5a
120
120
C4b
C5b
H5b
120
H7cl
C2a
C2a
C6b
C5b
H5b
120
C4c
C6c
C5c
C5c
H5c
H5c
C4d
C6d
C5d
H5d
H5d
C2b
C2b
ClOa
C12a
ClOc
C5d
C7a
C7a
CI la
Clla
Cllc
H7al
H7a2
Atom 3
C8s
C9s
H7al
Angle
111(1
98(2
109(2
109(2
109
ClOs
C9s
108
108
C7c
H7cl
H7c2
C7c
H7c2
C7d
H7dl
109
109
C7d
H7d2
109
C6d
C7d
H7dl
109
120
120
119
C6d
H7dl
C9a
C7d
C7d
ClOa
H7d2
H7d2
109
110
122
119
Clla
C9c
ClOa
HlOa
HlOa
ClOc
HlOc
ClOc
C15c
HlOc
H15c3
120
120
109
C15c
C2s
H15c3
H2sl
109
112
109
Hlla
109
120
Hlla
Hllc
120
120
Cllc
H15cl
H15c2
Ols
110
122
129
Bond Angles for Structure I (cont.)
Atom 3 Angle
Atom 1 Atom 2
120
C2s
Hllc
Ols
H13c
119
C3s
C2s
H13c
119
C3s
C2s
Atom 3
H2s2
H2sl
H2s2
Atom 1
C12c
C12c
C14c
Atom 2
Cllc
CI 3c
C13c
C12a
C14a
C9a
C13a
C13a
C13a
C14a
C14a
H13a
119
H13a
H14a
H14a
C9c
C13c
C14c
Angle
112
112
112
109
C2s
H2s2
119
121
121
H2s
C2s
C2s
C4s
C3s
C3s
C3s
H14c
121
C4s
C3s
H3sl
H3s2
H3sl
H3s2
113
C14c
H14c
121
H3s
C3s
H3s2
109
C12a
C15a
109
C3s
C4s
C15a
109
C3s
C4s
H4sl
H4s2
111
C12a
H15al
H15a2
111
C12a
C15a
C15a
C15a
H15a3
H15a2
H15a3
109
109
109
C5s
C5s
H4s
C4s
C4s
C4s
H4sl
H4s2
H4s2
111
111
109
C15a
H15a3
109
Ols
C5s
114
C12c
C12c
CI 5c
C15c
H15cl
H15c2
109
109
Ols
C4s
C5s
C5s
H5sl
H5s2
H5sl
114
C12c
C15c
H15c3
110
C4s
C5s
H5s2
114
H15cl
06s
C15c
H15c2
109
H5s
C5s
H5s2
109
C7s
H7sl
109
C8s
C9s
H9sl
110
06s
C7s
H7s2
109
C8s
C9s
H9s2
110
C8s
C8s
C7s
H7sl
H7s2
109
109
ClOs
C9s
110
ClOs
C9s
H9sl
H9s2
H7s2
109
C9s
H9s2
109
H8sl
H8s2
H8sl
112
112
112
H9sl
06s
06s
C9s
ClOs
ClOs
ClOs
HlOsl
H10s2
HlOsl
110
110
110
H15al
H15al
H15a2
H7sl
C7s
C7s
C9s
C7s
C7s
C8s
C8s
C8s
113
113
113
114
110
130
Atoml
08al
08a2
C9a
Ola
Ola
08al
08al
08a2
Torsion Angles for Structure I
Atom 2
Atom 3
Atom 4
S8a
Ola
Cla
S8a
Ola
Cla
S8a
Ola
Cla
S8a
C9a
ClOa
S8a
C9a
C14a
S8a
C9a
ClOa
S8a
C9a
C14a
S8a
C9a
ClOa
Angle
61.31(0.56)
-67.92(0.55)
177.08(0.51)
-68.89(0.79)
113.92(0.73)
43.60(0.86)
C9a
C14a
08c 1
S8a
S8a
-133.59(0.72)
177.05(0.74)
-0.14(0.85)
Olc
Clc
-45.71(0.60)
08c2
S8c
Olc
Clc
-174.17(0.53)
C9c
S8c
Clc
70.03(0.59)
Olc
01c
S8c
S8c
Olc
C9c
C9c
ClOc
C14c
08cl
S8c
C9c
-100.89(0.72)
84.80(0.75)
15.05(0.81)
08cl
08c2
S8c
C9c
C9c
08c2
S8c
S8c
S8a
S8a
08a2
S8c
S8c
04a 1
04al
04a2
04a2
04cl
04cl
04c2
ClOc
C14c
-159.26(0.69)
C9c
ClOc
C14c
149.10(0.69)
-25.21(0.85)
Ola
Cla
C2a
-90.95(0.71)
Ola
Olc
Olc
Cla
Clc
C6a
92.09(0.72)
C2c
C6c
-101.94(0.72)
80.69(0.79)
C3a
C5a
176.39(0.77)
N4a
N4a
Clc
C4a
N4a
C4a
C4a
N4a
N4c
N4c
N4c
C4a
C4c
C4c
C4c
C3a
C5a
C3c
C5c
C3c
-3.68(1.17)
-5.15(1.17)
174.78(0.81)
2.94(1.20)
-176.70(0.81)
-176.56(0.81)
131
Atoml
04c2
Atom 2
Ola
N4c
Cla
Atom 3
C4c
C2a
Atom 4
C5c
C3a
Angle
3.81(1.18)
176.46(0.66)
Ola
C6a
C6a
Cla
Cla
Cla
C2a
C2a
C2a
C7d
C3a
-7.44(1.09)
-6.73(1.16)
169.37(0.75)
Ola
Ola
C2a
Cla
Cla
Cla
Cla
Clb
C6a
C6a
C6a
C7d
C5a
C7a
C5a
-175.25(0.68)
6.98(1.12)
7.98(1.18)
C6a
C7a
-169.79(0.74)
Clb
C2b
C2b
C3b
C7a
177.52(0.67)
1.02(1.08)
C6b
Clb
C2b
C3b
-1.23(1.14)
C6b
C2b
C7a
Olb
Olb
Clb
Clb
Clb
C6b
C6b
C5b
-177.73(0.71)
-178.09(0.68)
1.59(1.09)
C2b
C2b
Clb
Clb
Olc
Clc
C6b
C6b
C2c
Olc
C6c
Clc
C2c
Clc
C2c
C6c
Clc
C2c
Olc
Olc
Clc
Clc
C6c
C7b
C5c
C6c
C7c
C2c
C2c
Clc
Clc >
Cld
Cld
Cld
Cld
C6c
C6c
C5c
C7c
C2d
C2d
C2d
C2d
C3d
C2a
Olb
01b
Old
Old
C6d
C6d
C7b
C5b
C7b
0.63(1.13)
C3c
175.83(0.69)
C7b
C3c
-8.58(1.10)
Clc
C3d
Clc
-179.69(0.70)
-6.96(1.21)
168.64(0.76)
-177.10(0.69)
6.24(1.15)
5.73(1.20)
-170.93(0.76)
176.21(0.71)
2.02(1.10)
-2.13(1.18)
-176.32(0.72)
132
Atoml
Old
C2d
C2d
Cla
•
Atom 2
Cld
Cld
Cld
C2a
Atom 3
C6d
C6d
C6d
C3a
Atom 4
C7d
C5d
C7d
C4a
Angle
2.31(1.12)
1.86(1.170
-179.36(0.73)
0.82(1.14)
C7d
Cla
C3a
C2a
C2a
C2a
C3a
C4a
-175.45(0.74)
C7d
C7d
C6d
C6d
-112.63(0.83)
63.40(0.96)
Clb
C2b
C3b
C4b
Cla
C2b
C3b
C4b
1.04(1.16)
177.57(0.74)
Clb
C2b
Cla
C6a
-68.93(0.97)
C3b
C2b
C2c
C2c
C7a
C6a
114.66(0.83)
C3c
C3c
C4c
C4c
1.58(1.17)
-174.11(0.75)
C2c
C7b
C6b
-107.90(0.85)
C2c
C7b
C6b
67.58(0.94)
C2d
C2d
C3d
C4d
C4d
1.32(1.24)
175.35(0.79)
-72.58(0.92)
Clc
C6c
C6c
C3a
C4a
N4a
113.42(0.85)
-176.49(0.72)
C2a
C3a
C4a
C5a
3.58 (1.26)
C2b
C2c
C3b
C3c
C4b
C4c
C5b
N4c
-0.26(1.26)
-174.92(0.74)
C2c
C3c
C4c
C5c
4.70(1.28)
C2d
N4a
C3a
C3d
C4a
C4a
C4d
C5a
C5a
C5d
C6a
C6a
-0.27(1.36)
177.78(0.74)
-2.29(1.29)
C3b
N4c
C4b
C4c
C5b
C5c
C6b
C6c
-0.37(1.24)
173.67(0.74)
Clc
C7b
Clc
C3c
' Cld
Clc
Cld
C3d
C2a
C2d
C2d
C3d
C7c
133
Torsion Angles for Structure I (cont.)
Atom 2
Atom 3
Atom 4
Atoml
C4c
C4d
C5a
Angle
-5.95(1.29)
0.00(1.38)
-3.33 (1.19)
174.50(0.77)
0.19(1.17)
C5c
C6c
C5a
C5d
C6a
C6a
C6d
Cla
C7a
C4b
C5b
C6b
Clb
C4b
C4c
C4c
C5b
C5c
C5c
C6b
C6c
C6c
C7b
Clc
Clc
-179.49(0.73)
0.79(1.18)
177.53(0.76)
C4d
C4d
C5d
C5d
C6d
C6d
Cld
C7d
-0.77(1.26)
-179.52(0.82)
Cla
C6a
C7a
C2b
108.77(0.86)
C5a
C6a
C7a
-68.94 (1.00)
Clb
C5b
C6b
C6b
C7b
VC7b
C2b
C2c
C2c
Clc
C5c
C6c
Clc
C2d
109.73(0.86)
C6c
Clc
-66.78 (0.98)
Cld
C7d
C5d
C6d
C6d
C2d
C2a
Cld
C2a
-111.03(0.86)
S8a
C14a
C9a
C9a
S8a
C3c
C9a
ClOa
ClOa
C14a
Clla
Clla
C13a
-177.64 (0.81)
-0.51(1.46)
178.96(0.77)
C4c
C5c
C6c
-5.95(1.29)
C3d
C4d
C5d
C6d
0.00(1.38)
C4a
C5a
C6a
Cla
-3.33 (1.19)
C4a
C5a
C6a
C7a
C4b
C4b
C4c
C4c
C5b
C5b
C5c
C5c
C6b
C6b
C6c
C6c
Clb
174.50(0.77)
0.19(1.17)
C3c
'C3d
C4a
C4a
C7b
Clc
Clc
70.14(0.92)
-110.18(0.81)
70.24(0.94)
-179.49(0.73)
0.79(1.18)
177.53(0.76)
134
Torsion Angles for Structure I (cont.)
Atom 2
Atom 3
Atom 4
Atoml
C4d
,C4d
Cla
C5a
C5d
C5d
C6a
C6a
C6d
C6d
C7a
C7a
Clb
C5b
Clc
C5c
C6b
C6b
C6c
C6c
C7b
Clc
Cld
C6d
C5d
S8a
VC7b
C7c
Cld
C7d
C2b
C2b
C2c
Angle
-0.77(1.26)
-179.52(0.82)
108.77(0.86)
-68.94 (1.00)
70.14(0.92)
Cld
C2c
C2d
C2d
C2a
70.24(0.94)
C6d
C7d
C2a
-111.03(0.86)
C9a
ClOa
Clla
-177.64 (0.81)
C14a
C9a
S8a
C9a
ClOa
S8c
C14c
C9a
C9c
C9c
ClOa
C14a
C14a
Clla
C13a
C13a
-0.51(1.46)
178.96(0.77)
1.85(1.44)
ClOc
ClOc
Cllc
Cllc
-170.07 (0.69)
4.08(1.32)
S8c
C9c
C14c
C13c
171.69(0.74)
ClOc
C9a
C9c
C14c
C13c
-2.50(1.37)
ClOa
Clla
C12a
-1.88(1.68)
C9c
ClOc
C12c
-2.36(1.36)
ClOa
ClOa
Clla
Clla
Cllc
C12a
C13a
C12a
C15a
2.95(1.84)
179.48(1.16)
ClOc
Cllc
C12c
C13c
-0.85(1.42)
ClOc
Clla
C15a
Cllc
C12a
C12c
C15c
C14a
176.45(0.90)
C12a
Cllc
C15c
C12c
C12a
C12c
C12c
C13c
C13a
C13a
C13c
C13c
C14c
C14a
C13a
-110.18(0.81)
109.73(0.86)
-66.78 (0.98)
C14a
-1.60(1.82)
-177.84(1.17)
C14c
C14c
C9c
C9a
2.45(1.51)
-174.85 (0.97)
-0.81(1.49)
-0.81(1.65)
APPENDIX
C
BOND LENGTHS, BOND ANGLES,
AND TORSION ANGLES FOR
STRUCTURE II
136
Bond Distances for Structure H
Distance A Atom 1
Atom 2
(e.s.d.)
Atom 1
Atom 2
S8a
S8a
Ola
08al
08a2
C9a
01c
1.427(5)
1.751(6)
1.593(5)
1.595(5)
1.427(6)
S8a
S8a
S8c
S8c
S8c
08c 1
1.431(6)
08c2
S8c
C9c
1.420(5)
1.742(6)
Ola
Cla
Clb
Clc
Clc
Cld
Cld
C2a
C2a
C2c
C6c
C2d
C6d
C3a
Distance A
(e.s.d.)
1.385(9)
1.398(9)
1.368(8)
1.41(1)
1.39(1)
1.511(9)
C2b
C7d
C3b
C2b
C7a
1.49(1)
1.432(8)
1.383(8)
C2c
C3c
1.40(1)
C2c
C7b
Old
041b
041d
Clc
Cld
1.422(8)
1.390(9)
C3d
C7c
1.53(1)
C41b
C41d
1.216(7)
1.226(7)
C2d
C2d
C3a
1.525(9)
1.401(9)
C3b
C4a
C4b
1.379(9)
1.39(1)
N4b
C4b
1.429(9)
C3c
C4c
N4b
C41b
1.352(9)
C3d
C4d
1.38(1)
1.39(1)
N4d
C4d
1.439(9)
C4a
C5a
1.38(1)
N4d
Cla
Cla
C41d
C2a
C6a
1.344(9)
C5b
C5c
1.381(8)
1.395(9)
1.388(9)
C4b
C4c
C4d
C5d
Clb
C2b
C6b
C6c
C5a
C5a
C6a
Clb
C5a
1.390(8)
1.41(1)
C5d
C6a
C6d
C7a
1.38(1)
1.393(9)
C12a
C12a
C6b
C6c
C7b
Clc
1.52(1)
1.505(8)
1.52 (1)
C12c
C12c
C13a
C6d
C7d
1.489(8)
C13c
Olb
01c
C6b
C13a
C15a
C13c
C15c
C14a
C14c
1.394(9)
1.37(1)
1.360(8)
1.39(1)
1.378(9)
1.38(1)
1.50(1)
1.38(1)
1.52(1)
1.384(9)
1.36(1)
137
Atom 1
Atom 2
C9a
C9a
C9c
C9c
ClOa
ClOc
CI la
Cllc
Olb
ClOa
C14a
ClOc
C14c
Clla
Cllc
C12a
C12c
Old
N4b
Hlb
Hid
H4b
N4d
C3a
H4d
H3a
C3b
C3c
H3b
H3c
C3d
C4a
H3d
H4a
C4c
C5a
H4c
H5a
C5b
C5c
H5b
H5c
C5d
C7a
H5d
H7al
,C7a
C7b
C7b
C7c
C7c
Bond Distances for Structure II (cont.)
Distance A Atom 1
Atom 2
(e.s.d.)
1.360(9)
1.39(1)
1.37(1)
1.39(1)
1.375(9)
1.38(1)
C41b
C41d
Cls
Cls
Cls
C2s
C42
C42
Cll
C12
C13
C14
Distance A
(e.s.d.)
1.50(1)
1.50(1)
1.774(8)
1.750(9)
1.718(8)
1.734(9)
1.39(1)
C2s
C2s
C15
1.76(1)
C16
1.743(8)
0.95
1.39(1)
0.95
ClOa
HlOa
HlOc
0.95
Hlla
0.95
Hllc
H13a
0.95
0.95
Cllc
C13a
0.95
0.95
C13c
HI 3c
0.95
0.95
0.95
C14a
C14c
H14a
0.95
H14c
0.95
C15a
H15al
0.95
0.85
0.95
C15a
C15a
H15a2
1.06
0.99
1.16
ClOc
Clla
0.95
0.95
C15c
0.95
H15a3
0.95
0.95
C15c
H15cl
H15c2
0.95
0.95
C15c
H15c3
0.95
0.95
C42b
H42bl
0.84
H7a2
0.95
C42b
H42b2
0.95
H7bl
H7b2
H7cl
H7c2
0.95
H42b3
0.95
0.95
0.95
C42b
C42d
C42d
H42d2
H42d3
1.00
0.95
0.95
C42d
H42d3
0.95
0.92
138
Atom 1
Atom 2
C7d
C7d
H7dl
H7d2
Bond Distances for Structure II (cont.)
Atom 2
Distance A Atom 1
(e.s.d.)
His
0.95
Cls
H2s
0.95
C2s
Atom 1
Atom 2
Ola
Ola
Ola
08al
S8a
S8a
Bond Angles for Structure II
Atom 1 Atom 2
Atom 3 Angle
Clc
108.8(3) Olc
08al
Clc
102.5(3) Olc
08a2
S8a
C9a
S8a
S8a
08a2
S8a
Olc
Olc
S8c
S8c
Olc
Distance A
(e.s.d.)
0.95
0.95
Atom 3
Angle
C2c
C6c
118.2(6)
118.4(6)
103.8(3) C2c
120.8(3) Old
Clc
Cld
C6c
123.2(6)
C2d
121.1(6)
Cld
C6d
C6d
117.4(5)
C9a
109.0(3) Old
110.5(3) C2d
109.2(3) Cla
103.4(3) Cla
103.9(3) C3a
C2a
C2a
S8c
08c 1
08c2
G9c
C2a
08cl
S8c
08c2
119.5(3) Clb
C2b
08cl
08c2
S8c
S8c
C9c
C9c
108.6(3) Clb
111.0(3) C3b
S8a
Ola
Cla
S8c
C4b
C4d
Olc
N4b
N4d
Ola
Cla
Clc
C41b
C41d
C2a
118.9(4) Clc
118.7(4) Clc
125.8(6) C3c
Ola
C2a
Cla
C6a
Cla
Olb
Clb
08al
08a2
C9a
Cld
C3a
C7d
C7d
121.5(6)
115.8(6)
123.5(6)
120.1(6)
117.6(6)
C2b
C2b
C3b
C7a
C7a
C2c
C3c
116.8(6)
C2c
C2c
C7b
C7b
123.5(6)
124.8(5) Cld
C2d
117.9(5) Cld
117.5(6) C3d
C2d
C2d
C3d
C7c
C6a
124.5(6) C2a
C2b
121.6(6) C2b
120.6(6)
121.8(5)
119.5(6)
119.2(6)
120.6(6)
C7c
120.2(5)
C3a
C4a
121.8(6)
C3b
C4b
121.3(6)
139
Bond Angles for Structure II (cont.)
Atom 3 Angle
Atom 1 Atom 2
C3c
116.6(5) C2c
C6b
Atom 1
Atom 2
Olb
C2b
Clb
Clb
C3a
N4b
N4b
C3b
C3c
N4d
C4a
C4b
C4b
C4b
C4c
C4d
N4d
C3d
C4a
C4d
C4d
C5a
C3d
C5d
C5d
C6a
C4b
C4c
C5b
C5c
C6b
C6c
C4d
Cla
C5d
C6a
C6a
C6d
C5a
C6a
Clb
C6b
C5a
C3b
C5b
C5b
C5c
121.6(6) C2d
C3d
Atom 3
C4c
C4d
119.8(6)
117.9(5)
122.0(6)
119.9(6)
Cld
C5d
C2b
C2c
C6d
C6d
C7a
C7d
C7d
C6a
120.6(7)
116.8(5)
122.6(6)
120.5(6)
C2d
C2a
C7b
C7c
C6b
C6c
C7d
C9a
C6d
S8a
S8a
Angle
120.9(7)
119.7(6)
120.5(6)
121.6(6)
112.8(5)
110.5(6)
111.7(5)
110.4(6)
ClOa
C14a
C14a
120.1(6)
118.6(5)
C9c
ClOc
C14c
C14c
119.0(6)
119.8(5)
120.7(6)
C9a
121.4(6) ClOa
120.5(6) S8c
C9a
C9c
120.8(7) S8c
121.3(7) ClOc
116.4(6) C9a
C9c
ClOa
Clla
120.6(7)
C7a
123.0(6) C9c
120.4(6) ClOa
ClOc
Clla
Cllc
C12a
119.3(7)
120.1(7)
C6b
C5b
118.9(6) ClOc
Cllc
C12c
120.8(7)
Clb
C6b
C7b
119.2(6) Clla
C12a
C13a
118.4(6)
C5b
C6b
C7b
121.7(6) CI la
C12a
C15a
120.4(7)
Clc
C6c
C5c
117.3(6) C13a
C15a
Clc
C5c
C6c
C6c
C7c
C7c
C13c
C15c
Cld
C12a
C12c
C6d
C12c
C15c
121.2(7)
118.6(7)
119.7(7)
121.8(8)
121.9(7) 041d
121.5(8) N4d
C41d
C41d
C42d
C13c
C5d
C14a
C14c
123.1(6) Cllc
119.5(6) Cllc
117.8(5) C13c
C12a
C12c
C12c
C42d
121.9(7)
113.9(5)
C9a
C14a
C13a
117.9(6) Cll
Cls
a2
109.6(5)
Cla
C5a
C13a
C7a
121.0(6)
140
Atom 1
C9c
C(c
041b
041b
Atom 2
C14c
C14c
C41b
C41b
Atom 3
C13c
C13c
N4b
C42b
Angle
119.1(6)
119.1(6)
123.5(6)
122.6(7)
N4b
C41b
C41d
C42b
113.9(6) C14
124.1(6) C15
C2s
Atom 3
C13
C13
C13
C15
C16
C2s
C16
121
108
C4c
C6c
C5c
H5c
H5c
127
C4d
C5d
041d
Clb
N4d
Hlb
Atom 1
Cll
Cll
C12
C14
Atom 2
Cls
Cls
Cls
C2s
Angle
110.1(5)
110.1(5)
111.5(4)
110.5(4)
110.5(5)
110.2(5)
120
Cld
C4b
C41b
Olb
Old
N4b
Hid
H4b
N4b
H4b
107
C6d
C5d
C4d
N4d
H4d
124
C2b
C7a
C41d
C2a
N4d
C3a
H4d
H3a
111
119
C2b
C6a
C7a
C7a
C4a
C3a
H3a
119
C6a
C7a
H7al
H7a2
C2b
C4b
C3b
H3b
H7a2
H3b
H7al
C2c
C7a
C3b
119
119
C7b
H7bl
110
109
C2c
C3c
H3c
120
C2c
C7b
H7b2
109
C4c
C3c
H3c
120
C6b
c7b
H7bl
C2d
C4d
C3a
C5a
C3s
C3d
C3d
H3d
H3d
120
120
C6b
H7bl
C7b
C7b
H7b2
H7b2
109
109
110
C4a
H4a
120
C7c
C4a
C4c
H4a
H4c
120
120
C2d
C2d
C7c
C6c
C7c
H7cl
H7c2
H7cl
109
109
C4c
C5a
H4c
H5a
H5a
120
119
119
C6c
H7c2
109
H7cl
C2a
C7c
C7c
H7c2
C7d
H7dl
H5b
H5b
120
120
C2a
C6d
H7d2
109
H15al
C7d
C7d
C15a
H7dl
H7dl
H15a3
110
109
109
109
C5c
C4a
C6a
C4b
C6b
C6d
C5a
C5b
C5b
C7d
C5c
H5d
H5d
H7al
H7a2
120
119
119
109
109
109
109
109
108
141
Atom 1
Atom 2
Atom 3
H7dl
C9a
C7d
ClOa
ClOa
ClOc
ClOc
Clla
H7d2
HlOa
HlOa
HlOc
HlOc
Hlla
HI la
Hllc
Hllc
H13a
Clla
C9c
Cllc
ClOa
C12a
ClOc
C12c
C12a
C14a
Clla
Cllc
Cllc
C13a
Angle
110
120
120
120
120
120
120
120
Atom 1
H15a2
CI 2c
C12c
C12c
H15cl
H15cl
Atom 2
C15a
CI 5c
C15c
C15c
C15c
Atom 3
H15a3
H15cl
H15c2
H15c3
H15c2
Angle
110
119
107
107
107
C15c
H15c3
107
H15c2
C15c
C42b
H15c3
H42bl
110
110
C42b
C42b
H42b2
H42b3
109
109
H42b2
H421b3
109
110
119
C41b
C41b
C41b
120
H13a
119
H42bl
C12c
C13a
C13c
H13c
119
H42b2
C42b
C42b
C9a
C14a
H14a
121
C41d
C42d
H42dl
122
C13a
C14a
H14a
121
C41d
C42d
H42d2
106
C9c
C13c
C14c
C14c
H14c
H14c
121
121
C41d
H42dl
H42d3
H42d2
106
106
C12a
C15a
H15al
117
H42dl
C42d
C42d
C42d
H42d3
106
C12a
C12a
C15a
C15a
H15a2
H15a3
108
108
H42d2
Cll
C42d
Cls
H42d3
His
110
110
H15al
C13
C14
C15a
H15a2
His
H2s
108
108
108
C12
Cls
C2s
C2s
His
H2s
H2s
1081
Cls
C2s
C15
C16
109
109
142
Atom 1
08al
08a2
C9a
Ola
Ola
Atom 2
S8a
S8a
S8a
S8a
S8a
Torsion Angles for Structure II
Atom 3
Atom 4
Ola
Ola
Ola
C9a
C9a
Cla
Cla
Cla
ClOa
C14a
Angle
-36.93(0.46)
-165.86(0.42)
79.01(0.46)
-88.71 (0.62)
86.33(0.60)
S8a
C9a
ClOa
27.09(0.69)
C14a
-157.86(0.55)
162.03(0.59)
-22.92(0.69)
-37.38(0.47)
08al
08a 1
08a2
08a2
08c 1
S8a
S8a
S8a
C9a
C9a
C9a
ClOa
C14a
S8c
Olc
Clc
08c2
C9c
S8c
S8c
Olc
Olc
Clc
Clc
78.37(0.46)
Olc
•01c
S8c
C9c
C10C
-88.77(0.62)
S8c
C9c
C14c
83.66(0.61)
08cl
S8c
S8c
C9c
C9c
ClOc
C14c
27.43(0.69)
-160.15(0.57)
08c2
S8c
C9c
ClOc
160.69(0.58)
08c2
S8c
C9c
C14c
S8a
Ola
Cla
C2a
-26.89(0.70)
82.66(0.63)
S8a
Ola
C6a
-99.67(0.60)
S8c
S8c
Olc
Olc
Cla
Clc
Clc
Clc
C6c
84.82(0.64)
-100.47(0.61)
C41b
N4b
C4b
C3b
-138.52(0.67)
C41b
C4b
C5b
46.37(0.94)
C4b
N4b
N4b
C41b
041b
8.30(1.03)
C4b
N4b
C41b
C42b
-173.31(0.58)
C41d
C41d
N4d
N4d
C4d
C4d
C3d
C5d
149.55(0.68)
-32.64(1.03)
08c 1
-165.63(0.41)
143
|Atom 1
C 4 d
llC4d
ll01a
ll01a
|jC6a
|C6a
ll01a
01a
ll
|| C2a
Atom 2
Atom 3
N4d
N4d
Cla
Cla
Cla
Cla
Cla
Cla
C42d
C41d
C2a
C2a
C2a
Cla
Cla
Atom 4
041d
C42d
C3a
C7d
C3a
Angle
-5.77(1.11)
174.40(0.65)
-177.20(0.56)
11.24(0.95)
5.31(1.00)
-166.24(0.64)
C6a
C6a
C7d
C5a
C7a
177.64(0.56)
-7.53(0.94)
C6a
C5a
-4.87(1.01)
C6a
C7a
169.97(0.63)
C3b
C7a
C2a
|| C2a
ll01b
01b
ll
Clb
C2b
C2b
|C6b
Clb
C2b
C3b
-178.39(0.57)
2.41(0.94)
-3.89(0.95)
|C6b
lb
P01b
Clb
C2b
C7a
176.90(0.60)
Clb
Clb
C6b
C6b
C5b
C7b
178.03(0.57)
-6.23(0.88)
C2b
Clb
C6b
C5b
3.27(0.98)
jC2b
01c
Clb
Clc
C6b
C2c
C7b
C3c
179.01(0.60)
-178.99(0.57)
Clc
C2c
C7b
7.04(0.97)
Clc
C3c
6.58(1.01)
Clc
Clc
C2c
C2c
C6c
C7b
C5c
-167.39(0.64)
179.72(0.57)
Clc
C6c
C7c
-3.63(0.96)
Clc
Clc
C6c
C5c
-5.85(1.02)
C6c
C7c
Cld
Cld
C2d
C2d
C3d
C7c
170.79(0.64)
177.69(0.59)
-1.32(0.97)
ll
ll
ll01c
C6c
| C6c
01c
ll
ll01c
||C2c
|C2c
ld
P
||01d
Clb
144
Atom 1
j Atom 2
Atom 3
I Atom 4
Angle
|jC6d
1 Cld
C2d
1C 3 d
-1.45(1.00)
J|c6d
| Cld
C2d
1 C7c
179.55(0.60)
ll01d
| Cld
C6d
-178.30(0.57) I
Ifo id
||C2d
1 Cld
C6d
1 C5d
j C7d
1.07(0.93)
J
1 Cld
| Cld
C6d
1 C5d
0.87(0.99)
||
C6d
1 C7d
-179.76(0.63)
ll
Cla
| C2a
C3a
j C4a
-1.30(0.99)
||
ll
C7d
j C2a
C3a
j C4a
170.56(0.64
1
ll
Cla
1 C2a
C7d
| C6d
106.06(0.73)
|
||C3a
j C2a
C7d
j C6d
-65.15(0.81)
]
llClb
1 C2b
C3b
J C4b
2.09(0.96)
||
ll
C7a
1 C2b
C3b
1 C4b
-178.71(0.61)
ll
Clb
j C2b
C7a
1 C6a
78.82(0.78)
||C3b
| C2b
C7a
j C6a
-100.36(0.71) J
ll
Clc
1 C2c
C3c
j C4c
-1.66(1.01)
J
ll
C7b
1 C2c
C3c
j C4c
172.56(0.65)
|
ll
Clc
1 C2c
C7b
|c6b
107.82(0.74)
1
|[C3c
1 C2c
C7b
j C6b
-65.99(0.81)
||
llCld
1 C2d
C3d
1 C4d
1.43(0.99)
j
llC7c
1 C2d
C3d
J C4d
-179.56(0.61) j
llCld
I C2d
C7c
| C6c
77.04(0.79)
J|C3d
1 C2d
C7c
| C6c
-101.96(0.70) ||
||C2a
j C3a
C4a
j C5a
-2.81(1.06)
||c2b
1 C3b
C4b
1 N4b
-174.89(0.58) ||
||C2b
C4b
1 C5b
0.32(0.99)
1
|C2c
1 C3b
j C3c
C4c
1 C5c
-3.78(1.10)
1
|| C2d
| C3d
C4d
j N4d
177.00(0.59)
|
|C2d
1 C3d
C4d
j C5d
-0.86(1.01)
||
||C2d
J
|
|
|
1
145
Torsion Angles for Structure II (cont.)
Atom 1
C3a
N4b
Atom 2
C4a
C4b
Atom 3
C5a
C5b
C3b
C3c
N4d
C4b
C4c
C4d
C5b
C5c
C5d
C3d
C4a
C4a
C4d
C5a
C5a
C5d
C6a
C6a
Cla
C7a
C4b
C5b
C6b
Clb
-0.73(0.98)
C4b
C4c
C4c
C5b
C5c
C5c
C6b
C6c
C6c
C7b
Clc
C7c
-176.37(0.61)
0.09(1.01)
-176.68(0.65)
C5d
C6d
C5d
Cld
C7d
-0.27(1.00)
-179.63(0.63)
C2b
-112.23(0.72)
C2b
C2c
62.41(0.82)
C4d
C4d
Cla
C5a
C6a
C6d
C7a
C6a
C7a
Clb
C6b
C5b
Clc
C5c
C6b
C6c
C7b
C7b
Clc
C6c
C7c
C5d
C6d
C6d
S8a
C14a
S8a
S8c
C14c
S8a
Cld
Atom 4
C6a
C6b
C6b
C6c
C6d
C6d
C2c
C2d
Angle
3.31(1.06)
174.00(0.60)
174.00(0.60)
4.58(1.11)
-177.45(0.61)
0.28(1.04)
0.37(0.99)
-174.61(0.64)
-72.20(0.78)
103.42 (0.72)
-112.16(0.72)
64.42(0.80)
C7d
C2d
C2a
-75.97(0.78)
C7d
C2a
103.38(0.71)
C9a
ClOa
Clla
175.05(0.60)
C9a
C9a
ClOa
C14a
Clla
C13a
0.12(1.13)
C9c
C9c
ClOc
ClOc
C14c
Cllc
Cllc
C13c
C9c
-175.21(0.57)
0.49(1.12)
0.49(1.12)
-171.85(0.59)
146
Atom 1
ClOc
C9a
Clla
Atom 2
C9c
ClOa
ClOc
Clla
Clla
Cllc
Cllc
C12a
C15a
Atom 3
C14c
Clla
Atom 4
C13c
C12a
Cllc
C12a
C12a
C12c
C12c
C12c
C13a
C15a
C13c
C15c
C13a
C14a
Angle
0.44(1.11)
-1.59(1.17)
-2.31(1.20)
3.10(1.15)
-178.07(0.75)
3.15(1.22)
-177.23(0.78)
-3.26(1.17)
C12a
C13a
C14a
177.92(0.75)
Cllc
C15c
C12a
C12c
C12c
C14c
C14c
C9a
-2.22(1.22)
C13a
C13c
C13c
C14a
C12c
C13c
C14c
C9c
C9c
ClOa
ClOa
ClOc
ClOc
178.17(0.79)
1.82(1.13)
0.46(1.18)
APPENDIX
D
BOND LENGTHS, BOND ANGLES,
AND TORSION ANGLES FOR
STRUCTURE III
148
Atom 1
Atom 2
Distance A
(e.s.d.)
Atom 1
Atom 2
Distance A
(e.s.d.)
S
Ola
1.631(7)
C5a
C6a
1.48(1)
S
08a
1.391(9)
C5b
C6b
1.37(2)
S
08b
1.392(8)
C6a
C7a
1.51(1)
S
C9a
1.78(1)
C6b
C7b'
1.50(1)
Ola
Cla
1.40(1)
C8b
C9b
1.53(2)
|
Olb
Clb
1.39(1)
C9a
C14a
1.43(2)
1
04a
N4
1.42(1)
C9b
ClOb
1.29(1)
1
04b
N4
1.22(1)
C9b
C14b
1.35(2)
1
N4
C4a
1-19(1)
ClOa
Clla
1.32(2)
1
Cla
C2a
1.51(1)
ClOb
Cllb
1.40(2)
1
Cla
C6a
1.38(1)
CI la
C12a
1.46(2)
1
Clb
C2b
1.38(1)
CI lb
C12b
1.36(2)
1
Clb
C6b
1.37(1)
C12a
C13a
1.28(2)
J
C2a
C3a
1.38(1)
C12a
C15a
1.36(2)
1
C2a
C7b
1.30(1)
C12b
C13b
1.58(2)
1
C2b
C3b
1.54(1)
C13a
C14a
1.40(2)
1
C2b
C3b
1.37(1)
C13a
C14a
1.37(2)
|
C2b
C7a
1.54(1)
C13b
C14b
1.36(2)
1
C3a
C4a
1.37(1)
Cls
C2s
1.36(3)
1
C3b
C4b
1.38(2)
Cls
C5s
1.42(4)
1
C4a
C5a
1.33(1)
C2s
C3s
1.55(3)
1
C4b
C5b
1.40(2)
C3s
C4s
1.42(3)
1
C4s
C5s
1.44(4)
C7s
C8s
1.62(4)
1
C6s
C7s
1.42(3)
C8s
C8s'
1-57(3)
C3a
H3a
0.95
C14a
H14a
0.95
1
C3b
H3b
0.95
C14b
H14b
0.95
1
C4b
H4b
0.95
C15a
H15al
0.95
1
C5a
H5a
0.95
C15a
H15a2
0.95
1
149
Atom 1
Atom 2
Distance A
(e.s.d.)
Atom 1
Atom 2
Distance A
(e.s.d.)
C5b
H5b
0.95
C15a
H15a3
0.95
C7a
H7al
0.95
C2s
H2sl
0.95
C7a
H7a2
0.95
C2s
H2s2
0.95
C7b
H7bl
0.95
C3s
H3sl
0.95
C7b
H7b2
0.95
C3s
H3s2
0.95
C8b
H8bl
0.95
C4s
H4sl
0.95
C8b
H8b2
0.95
C4s
H4s2
0.95
ClOb
HlOa
0.95
C5s
H5sl
0.95
ClOb
HlOb
0.95
C5s
H5s2
0.95
Clla
Hlla
0.95
C7s
H7sl
0.95
CI lb
HI lb
0.95
C7s
H7s2
0.95
C12b
H12b
0.95
C8s
H8sl
0.95
C13a
H13a
0.95
C8s
H8s2
0.95
C13b
H13b
0.95
Atom 1
Atom 2
Bond Angles for Structure III
Atom 3
Angle
Atom 1 Atom 2
Ola
S
08a
101.9(5) C3b
C2b
C7a
119.7(8)
Ola
S
08b
109.6(4) C2a
C3a
C4a
120.1(9)
Ola
s
s
C9a
103.2(4)
C3b
C4b
122(1)
08b
122.7(5) N4
C4a
C3a
C9a
108.2(5) N4
C4a
C5a
08b
s
s
118.69
(9)
115.2(9)
C8a
109.4(5) C3a
C4a
C5a
125.9(9)
S
01A
C9a
116.0(5) C3b
C4b
C5b
119(1)
Clb
01B
Clb
113.8(7)
C4a
C5a
C6a
114.7(9)
04a
N4
08b
123(1)
C4b
C5b
C6b
119(1)
04a
N4
C4a
117.6(9) Cla
C6a
C5a
116.79
(9)
04b
N4
C4a
118(1)
C6a
C7a
128.4(9)
08a
08a
C2b
Cla
Atom 3
Angle
150
Atom 1
Atom 2
Atom 3
Angle
Atom 1
Atom 2
Atom 3
Angle
Ola
CI
C2a
119.2(8)
C5a
C6a
C7a
114.9(8)
Ola
Cla
C6a
116.9(8) Clb
C6b
C5b
119.6(9)
C2a
Cla
C6a
C7a
C6a
109.8(8)
Olb
Cla
C2b
122.8(9) C2b
120.4(8) C2a
C7b
C6b'
109.8(7)
Olb
Clb
C6b
117.5(8) Clb
C8b
C9b
113.2(9)
C2b
Clb
C6b
121.7(8) S
C9a
ClOa
116.2(8)
Cla
C2a
C3a
119.1(9) S
C9a
C14a
121.8(8)
Cla
C2a
C7b
119.8(8)
C9a
C14a
122(1)
C3a
C2a
C7b
121.0(9) C8b
C9b
ClOb
116(1)
Clb
C2b
C3b
117.7(9) C8b
C9b
C14b
123(1)
Clb
C2b
C7a
122.1(8) ClOb
C9b
C14b
121(1)
C9a
ClOa
CI la
117(1)
C9a
C14a
C13a
122(1)
C9b
ClOb
Cllb
119(1)
C9b
C14b
C13b
119(1)
ClOa
CI la
C12a
119(1)
C2s
Cls
C5s
96(2)
ClOb
CI lb
C12b
119(1)
Cls
C2s
C3s
102(2)
CI la
C12a
C13a
123(1)
C2s
C3s
C4s
98(2)
CI la
C12a
C15a
116(1)
C3s
C4s
C5s
98(2)
C13a
C12a
C15a
122(1)
Cls
C5s
C4s
91(2)
CI lb
C12b
C13b
120(1)
C6s
C7s
C8s
84(2)
C12a
C13a
C14a
118(1)
C7s
C8s
C8s'
75(2)
C12a
C13b
C14b
121(1)
C9b
C8b
H8bl
109
C2a
C3a
H3a
120
C9b
C8b
H8b2
109
C4a
C3a
H3a
120
H8bl
C8b
H8b2
109
C2b
C3b
H3b
119
C9a
ClOa
HlOa
122
C4b
C3b
H3b
119
Clla
ClOa
HlOa
122
C3b
C4b
H4b
120
C9b
ClOb
HI Ob
120
C5b
C4b
H4b
120
Cllb
ClOb
HlOb
120
C4a
C5a
H5a
123
ClOa
Clla
Hlla
121
C6a
C5a
H5a
123
C12a
Clla
Hlla
121
C3s
C4s
H4s2
112
H8sl
C8s
H8s
109
ClOa
151
Atom 1
C4b
C6b
C2b
Atom 2
C5b
C5b
C7a
C2b
C6a
C6a
C7a
C7a
C7a
H7al
C2a
C2a
C7a
C7b
C7b
C6b'
Atom 3
H5b
H5b
H7al
H7a2
Angle
120
120
109
Atom 1
C5s
ClOb
C12b
CI lb
Atom 2
C4s
CI lb
Cllb
C12b
C13a
C13a
C13b
Atom 3
H4sl
Hllb
HI lb
H12b
H12b
H13a
H13a
H13b
121
120
120
121
121
120
Angle
112
121
H7b2
109
109
109
109
109
109
C14a
C12b
C14b
C13b
H13b
120
C7b
H7bl
109
C9a
C14a
H14a
119
C6b'
C7b
H7b2
109
C13a
C14a
H14a
119
H7b
Olb
01b
C7b
H7b2
109
C9b
H14b
C12a
C8b
C8b
C15a
H8bl
H8b2
H15a2
109
109
109
C13b
C12a
C5s
C12a
C15a
H15a3
109
H4sl
C14b
C14b
C15a
C4s
C4s
H4s
120
120
109
112
109
H15al
C15a
H15a2
109
Cls
C5s
H5s
114
H15al
H15a2
C15a
H15a3
109
C5s
H5s
114
C15a
C2s
H15a3
C5s
H5s
H2sl
109
111
Cls
C4s
C4s
C5s
H5s
114
114
111
111
H5sl
C6s
C5s
H5s
H7s
115
H7s
115
Cls
H7al
H7a2
H7a2
H7bl
C13b
C12a
C12b
H14b
H15al
H4s
Cls
C3s
C3s
C2s
H2s2
C2s
C2s
H2sl
H2s2
111
C6s
C7s
C7s
H2sl
C2s
H2s2
109
C8s
C7s
H7s
115
C2s
C2s
C4s
C4s
C3s
C3s
C3s
C3s
C3s
C4s
H3sl
H3s2
112
112
112
112
109
112
C8s
H7sl
C7s
C7s
C8s'
C8s'
C7s
C7s
C8s
C8s
C8s
H7s
H7s
H8s
H8s
115
109
117
117
117
117
H3sl
C3s
H3sl
H3s2
H3s2
H4sl
C8s
H8s
H8s
II
II
II
II
II
II
109
|
|
152
I
Atoml
| 08a
| 08b
J C9a
Ola
[Ola
| 08a
Atom 2
S
S
s
Atom 3
Ola
Ola
Atom 4
Cla
Cla
Cla
Angle
1
-167/93(0.64)
-36.57(0.70)
s
s
Ola
C9a
C9a
ClOa
C14a
08b
08b
S
s
s
s
C9a
C9a
C9a
ClOa
ClOa
C14a
76.60(0.96)
I
156.33(0.84) [
20.46(0.96)
-166.73(0.88)
Ola
Cla
C2a
-106.44(0.80)
S
Ola
Cla
C6a
85.09(0.86)
C8b
01b
Clb
C2b
C8b
01b
Clb
Clb
04a
01b
N4
C8b
C4a
C6b
C9b
C3a
-72.25(1.06)
114.79(0.94)
-73.66(1.05)
-175.05(0.96)
04a
N4
N4
C4a
C4a
C5a
-0.75(1.39)
C3a
14.38(1.45)
N4
Cla
Cla
C4a
C2a
C5a
C3a
C2a
C7b
-171.32(0.99)
-175.46(0.82)
0.03(1.24)
Cla
C2a
C3a
-7.71(1.42)
Cla
Cla
C2a
C7b
167.79(0.88)
C6a
C5a
176.86(0.76) 1
04b
04b
Ola
Ola
C6a
C6a
79.93(0.66)
-96.21(0.83)
Ola
Ola
C2a
1C2a
101b
I
Cla
C6a
C7a
-2.25(1.42)
Cla
Cla
Clb
C6a
C5a
C7a
8.85(1.35)
I01b
1C6b
(26b
Clb
Clb
Clb
C6a
C2b
J
-170.26(0.93)
177.23(0.82) ||
C2b
C2b
C3b
C7a
C3b
-10.40(1.31)
-10.11(1.37)
C2b
C7b
162.26(0.88)
1
153
Atoml
Atom 2
Atom 3
Atom 4
Angle
Olb
Clb
C6b
C5b
-177.79(0.87)
01b
Clb
C6b
C7b'
2.47(1.25)
C2b
Clb
C6b
C5b
9.34(1.44)
C2b
Clb
C6b
C7b'
-170.40(0.87)
Cla
C2a
C3a
C4a
0.37(1.44)
C7b
C2a
C3a
C4a
-175.06(0.89)
Cla
C2a
C7b
C6b'
-131.19(0.90)
C3a
C2a
C7b
C6b'
44.22(123)
Clb
C2b
C3b
C4b
7.01(1.50)
C7a
C2b
C3b
C4b
-165.55(0.97)
Clb
C2b
C7a
C6a
-59.40(1.15)
C3b
C2b
C7a
C6a
112.82(1.00)
C2a
C3a
C4a
N4
179.40(0.91)
C2a
C3a
C4a
C5a
5.77(1.61)
C2b
C3b
C4b
C5b
-3.15(1.68)
N4
C4a
C5a
C6a
-178.01(0.83)
C3a
C4a
C5a
C6a
-4.19(1.49)
C3b
C4b
C5b
C6b
2.10(1.68)
, C4a
C5a
C6a
Cla
-2.92(1.30)
C4a
C5a
C6a
C7a
176.31(0.87)
C4b
C5b
C6b
Clb
-5.10(1.57)
C4b
C5b
C6b
C7b'
174.63(1.00)
Cla
C6a
C7a
C2b
121.76(1.04)
C5a
C6a
C7a
C2b
-57.37(1.07)
Clb
C6b
C7b'
C2a'
74.86(1.09)
C5b
C6b
C7b'
C2a'
-104.87(1.10)
Olb
C8b
C9b
ClOb
-102.96(1.15)
Olb
C8b
C9b
C14b
82.77 (1.31)
S
C9a
ClOa
Clla
175.22(0.85)
154
Atoml
Atom 2
Atom 3
Atom 4
Angle
C14a
C9a
ClOa
Clla
2.39(1.63)
S
C9a
C14a
C13a
-175.76(0.87)
ClOa
C9a
C14a
C13a
-3.33(1.69)
C8b
C9b
ClOb
Cllb
-177.14(1.12)
C14b
C9b
ClOb
Cllb
-2.77(1.80)
C8b
C9b
C14b
C13b
-178.88(1.14)
ClOb
C9b
C14b
C13b
7.16(1.80)
C9a
ClOa
Clla
C12a
-0.13(1.65)
C9b
ClOb
Cllb
C12b
1.77(2.06)
ClOa
Clla
C12a
C13a
-1.21(1.78)
ClOa
Clla
C12a
C15a
-174.01(1.06)
ClOb
Cllb
V12b
VI 3b
-5.11(2.22)
CI la
C12a
C13a
C14a
0.43(1.77)
C15a
C12a
C13a
C14a
172.80 (1.07)
C12a
C13a
C14a
C9a
1.91(1.72)
C12b
C13b
C14b
C9b
-10.55(1.99)
APPENDIX
E
BOND LENGTHS, BOND ANGLES,
AND TORSION ANGLES FOR
STRUCTURE XV
156
Atom 1
S8a
S8a
S8a
S8a
Ola
Olb
01b
04a
04b
N4
Cla
Cla
Clb
Clb
C2a
C2a
C2b
C2b
C3a
C3b
C3a
C3b
C4b
C5a
C5b
C7a
C7a
C7b
C7b
C8b
Atom 2
Ola
08a
08b
C8a
C9a
Clb
C8b
N4
N4
C4a
C2a
C6a
C2b
C6b
C3a
C7b
C3b
C7a
C4a
C4b
H3a
H3b
H4b
H5a
H5b
H7al
H7a2
H7bl
H7bl
H8bl
Distance A
1.602(4)
1.422(6)
1.423(5)
1.734(7)
1.424(7)
1.395(7)
1.431(9)
1.220(8)
1.220(8)
1.470(8)
1.384(9)
1.397(9)
1.385(7)
1.400(7)
1.399(9)
1.51(1)
1.390(9)
1.517(8)
1.37(1)
1.374(8)
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
Atom 1
C4a
C4b
C5a
C5b
C6a
C6b
C8a
C9a
C9a
C9b
C9b
ClOa
ClOb
Clla
Cllb
C12a
C12a
C12b
C13a
C13b
ClOb
Clla
Cllb
C12b
C13a
C13b
C14a
C14b
C15a
C15a
Atom 2
C5a
C5b
C6a
C6b
C7a
C7b'
C9b
ClOa
C14a
ClOb
C14b
Clla
Cllb
C12a
C12b
C13a
C15a
C13b
C14a
C14b
HlOb
Hlla
Hllb
H12b
H13a
H13b
H14a
H14b
H15al
H15a2
Distance A
1.37(1)
1.377(8)
1.386(9)
1.379(9)
1.51(1)
1.51(1)
1.49(1)
1.39(1)
1.365(8)
1.36(1)
1.39(1)
1.41(1)
1.42(1)
1.36(1)
1.38(1)
1.36(1)
1.53(1)
1.31(1)
1.39(1)
1.38(1)
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
0.95
157
[Atom 1
C8b
IClOa
Atom 2
H8b2
HlOa
Bond Distances for Structure IV (cont.)
Distance A Atom 1
Atom 2
0.95
C15a
H15a3
0.95
Distance A
0.95
Atom 1
Atom 2
Atom 3
Angle
Atom 1
Atom 2
Atom 3
Angle
Ola
S8a
08a
108.1
C3b
C2b
C7a
119.8
Ola
S8a
08b
109.4
C2a
C3a
C4a
119.5
Ola
S8a
C9a
98.1
C2b
C3b
C4b
120.3
08a
S8
08b
118.2
N4
C4a
C3a
118.9
08a
S8a
C9a
110.6
N4
C4a
C5a
117.7
08b
S8a
C9a
110.6
C3a
C4a
C5a
123.4
S8a
Ola
Cla
118.1
C3b
C4b
C5b
120.1
Clb
Olb
Clb
113.2
C4a
C5a
C6a
119.3
04a
N4
08b
123.0
C4b
C5b
C6b
121.7
04a
N4
C4a
118.2
Cla
C6a
C5a
116.4
04b
N4
C4a
118.8
Cla
C6a
C7a
123.0
Ola
Cla
C2a
118.8
C5a
C6a
C7a
120.4
Ola
Cla
C6a
116.0
Clb
C6b
C5b
117.2
C2a
Cla
C6a
125.2
Clb
C6b
C7b'
121.5
01b
Clb
C2b
119.9
C5b
C6b
C7b'
121.3
Olb
Clb
C6b
117.9
C2b
C7a
C6a
112.4
C2b
Clb
C6b
122.0
Cla
C7b
C6b'
114.1
Cla
C2a
C3a
115.9
08b
C8b
C9b
110.2
Cla
C2a
C7b
123.2
S8a
C9a
ClOa
117.2
C3a
C2a
C7b
120.9
SlOa
C9a
C14a
121.3
Clb
C2b
C3b
118.4
C8b
C9a
C14a
121.4
Clb
C2b
C7a
121.8
C8b
C9b
ClOb
122.8
ClOb
C9b
C14b
118.9
C13a
C12a
C15a
120.5
C9a
ClOa
CI la
117.0
Cllb
C12b
C13b
120.9
C9b
ClOb
CI lb
121.0
C12b
C13b
C14a
121.6
158
JjAtom 1
ClOa
Atom 2
Atom 3
Angle
Atom 1
Atom 2
Atom 3
Clla
C12a
122.5
C12b
C13b
C14b
j Angle
ClOb
CI lb
C12b
117.9
C9a
C14a
C13a
119.2
CI la
C12a
C13a
118.2
C9b
C14b
C13b
118.8
C2a
C3a
H3a
120
C9b
C8b
H8bl
109
C4a
C3a
H3a
120
C9b
C8b
H8b2
jjC2b
C3b
H3b
120
H8bl
C8b
H8b2
C4b
C3b
H3b
120
C9a
ClOa
HlOa
|[C3b
C4b
H4b
120
Clla
ClOa
HlOa
C5b
C4b
H4b
120
C9b
ClOb
HlOb
C5a
H5a
120
CI lb
ClOb
HlOb
C6a
C5a
H5a
120
ClOa
Clla
HI la
||C4b
C5b
H5b
119
C12a
Clla
HI la
C6b
C5b
H5b
119
ClOb
CI lb
Hllb
C7a
H7al
109
C12b
Cllb
Hllb
C7a
H7a2
109
CI lb
C12b
H12b
C6a
C7a
H7al
109
C13b
C12b
H12b
||C6a
C7a
H7a2
109
C12a
C13a
H13a
H7al
C7a
H7a2
110
C14a
C13a
H13a
C2a
C7b
H7bl
108
C12b
C13b
H13b -
||C2a
C7b
H7bl
108
C14b
C13b
H13b
H 7 b
C7b
H7bl
110
C9a
C14a
H14a
H 7 b
C7b
C6b'
108
CI 3a
C14a
H14a
C7b
C6b'
108
C9b
C14b
H14b
C8b
H8bl
109
C13b
C14b
H14b
C8b
H8b2
109
C12a
C15a
H15al
C15a
hl5a2
109
H15al
C15a
C12a
C15a
H15a3
109
H15a2
C15a
||H15al
CI 5a
H15a2
109
ll
C4a
|c2b
C2b
ll
01b
ll l b
H 7 b
P
|ci2a
H15a3
H15a3
|
122,5
1
109
I
110
122
122
1
120
1 119
1
121
1 121
1 120
1
119
1 119
1119
119
1 120
1 120
1
120
119
120
121
121
109
1109
j
' 109
I
1
I
I
I
11
I
I
1I
I
I
1I
I
159
Atoml
08a
|j08b
C 9 a
| Ola
Pla
|08a
108a
j 08b
||o8b
|jS8a
S8av
C8b
C8b
C l b
04a
j 04a
|| 04b
Io4b
Ola
Pla
||c6a
C6a
ola
l
Ola
|c2a
C2a
Olb
[Olb
C6b
C6b
Olb
Atom 2
S8a
S8a
S8a
S8a
S8a
S8a
S8a
S8a
S8a
Ola
Ola
Olb
Olb
Olb
N4
N4
N4
N4
Cla
Cla
Cla
Cla
Cla
Cla
Cla
Cla
Clb
Clb
Clb
Clb
_[_Clb
for Structure IV
Atom 3
Atom 4
Ola
Cla
Ola
Cla
Ola
Cla
C9a
ClOa
C9a
C14a
C9a
ClOa
C9a
C14a
C9a
ClOa
C9a
C14a
Cla
C2a
Cla
C6a
Clb
C2b
Clb
C6b
C8b
C9b
C4a
C3a
C4a
C5a
C4a
C3a
C4a
C5a
C2a
C3a
C2a
C7b
C2a
C3a
C2a
C7b
C6a
C5a
C6a
C7a
C6a
C5a
C6a
C7a
C2b
C3b
C2b
Cla
C2b
C3b
C2b
C7a
11C6b
C5b
Angle
I
I
II
-85.79(0.48) |
44.17(0.51)
159.41(0.47)
-138.25(0.59)
45.71(0.63)
108.92(0.61)
-67,12(0.63)
-23.99(0.67)
159.97(0.57)
91.17(0.56)
-92.43(0.52)
-90.90(0.67)
92.06(0.66)
-178.66(0.45)
12.34(0.77)
-166.24(0.53) |
-165.61(0.53)
15.82(0.77)
-178.22(0.45)
2.50(0.76)
5.75(0.80)
||
E>
-173.53(0.51)
176.99(0.45)
-7.78(0.74)
-6.87(0.81)
168.36(0.52)
178.80(0.58)
-1.33(0.97)
-4.29(1.00)
175.58(0.62)
[_-177.72(0.57^) II
160
Atoml
Olb
C2b
C2
Cla
C7b
Cla
C3a
Clb
C7a
Clb
C3b
C2a
C2a
C2b
N4
C3a
C3b
C4a
C4a
C4b
C4b
Cla
C5a
Clb
C5b
C2a
C2a
Olb
Olb
S8a
C14a
Atom 2
Clb
Clb
Clb
C2a
C2a
C2a
C23a
C2b
C2b
C2b
C2b
C3a
C3a
C3b
C4a
C4a
C4b
C5a
C5a
C5b
C5b
C6a
C6a
C6b
C6b
C7b
C7b
C8b
C8b
C9a
C9a
Atom 3
C6b
C6b
C6b
C3a
C3a
C7b
C7b
C3b
C3b
C7a
C7a
C4a
C4a
C4b
C5a
C5a
C5b
C6a
C6a
C6b
C6b
C7a
C7a
C7b'
C7b'
C6b'
C6b'
C9b
C9b
ClOa
ClOa
Atom 4
C7b'
C5b
C7b'
C4a
C4a
C6b'
C6b'
C4b
C4b
C6a
C6a
N4
C5a
C5b
C6a
C6a
C6b
Cla
C7a
Clb
C7b'
C2b
C2b
C2a'
C2a'
Clb'
C5b'
ClOb
C14b
CI la
Clla
Angle
4.08(0.93)
5.31(0.98)
-172.89(0.62)
-0.18(0.76)
179.12(0.50)
60.51(0.73)
-118.74(0.59)
0.29(1.02)
-179.58(0.65)
-60.02(0.81)
119.85(0.66)
177.48(0.48)
-4.04(0.85)
2.49(1.10)
-178.62(0.48)
2.88(0.86)
-1.38(1.11)
2.35(0.77)
-173.02(0.51)
-2.42(1.02)
175.78(0.66)
-64.19(0.70)
110.85(0.62)
67.75(0.80)
-110.37(0.69)
67.75(0.80)
-110.37(0.69)
7.19(0.80)
-174.75(0.53)
-176.10(0.66)
-0.07(1.14)
161
Torsion Angles for Structure IV (cont.)
Atom 2
Atom 3
Atom 4
Atoml
Angle
S8a
C9a
C14a
C13a
175.94(0.59)
ClOa
C9a
C14a
C13a
0.07(1.08)
C8b
C9b
ClOb
Cllb
177.86(0.60)
V14b
C9b
ClOb
Cllb
-0.19(0.95)
C8b
C9b
C14b
C13b
-178.32(0.62)
ClOb
C9b
C14b
C13b
-0.19(0.98)
C9a
ClOa
Clla
C12a
-0.04(1.49)
C9b
ClOb
Cllb
C12b
0.41(1.02)
ClOa
Clla
C12a
C13a
0.14(1.48)
ClOa
Clla
C12a
C15a
178.49(0.97)
ClOb
Cllb
C12b
C13b
-0.25(1.10)
CI la
C12a
C13a
C14a
-0.14(1.37)
C15a
C12a
C13a
C14a
-178.50(0.90)
CI lb
C12b
C13b
C14b
-0.13(1.20)
C12a
C13a
C14a
C9a
0.03(1.08)
C12b
C13b
C14b
C9b
0.36(1.13)
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