Preparation and Reactions of Sulfur-Nitrogen Ring Systems*
HERBERT
W .
ROESKY
Anorganisch-chemisches Institut der Universität Frankfurt
(Z. Naturforsch. 31 b. 680-683 [1976]; received August 12, 1975)
X-ray, Sulfur-nitrogen Ring Systems, Silicon
Two routes for the preparation of (CH3)2SnS2N2 are given, which are kinetically
controlled reactions. The molecule (CH3)2SnS2N2 was characterized by X-ray analysis. It
is an interesting starting material for the preparation of S2N2CO and S3N20. The latter
reacts with iminosulfur oxides and isocyanates under the formation of S3N3SO2F and
S3N3SO2CF3. The structure of S3N3SO2F was established by X-ray analysis. The bonding
properties are discussed.
The cleavage of thin-nitrogen derivatives with S3N2CI2 yields also five membered sulfurnitrogen rings. The structure and properties of P3N3F5NS3N2 and C3N3F2NS3N2 are reported. Six, eight and ten membered rings are formed by the reactions of
(CH 3 ) 3 Si-N = S = N-Si(CH 3 ) 3
with F S 0 2 - N = S = 0 , these are S4N4O2 and S 5 N5 + S 3 N30 4 -, respectively. The cation S5N5+
is a planar molecule, while the oxygen containing species are puckered. In S 4 N 4 02 the
oxygens are attached to one sulfur atom, which has a tetrahedral configuration.
The structure of the silicon containing cyclic and bicyclic rings (CH3)2Si(NSN)2Si(CH3)2
and CH3Si(NSN)3SiCH3 were determined.
A l t h o u g h tetrasulfur tetranitride was prepared
140 years ago, little is k n o w n about other kinetically
controlled reactions in this
m e t h o d for preparing
S4N4
field1.
monia.
SCI3
in
chlorine.
"SC13"
-
tetrachloride
SCI2
solution
S
CH,
"Sn
CH,'
with am-
is n o t k n o w n and therefore
carbon
2 S2CI2 + 2 N[Sn(CH3)3]3
is the reaction o f sulfur
chlorides having a composition
treated
The preferred
+
(CH3)4Sn + 4(CH 3 ) 3 SnCI +
\
is
with
B y using N[Sn(CH 3 ) 3 ] 3 as a nucleophile, it is also
possible t o get t o the same product according t o the
4 SCI3 + 16 NH3
S 4 N 4 + 1 2 NH4CI
following equations 3 - 4 .
R e c e n t l y we used tin substitued amines instead
o f a m m o n i a because the N - H (391 k J m o l - 1 ) b o n d
S4N4 + 2 N[Sn(CH3)3]3
3 (CH 3 ) 3 Sn-N=S = N-Sn(CH 3 ) 3
M
energy is significantly greater than the tin-nitrogen
S
b o n d energy (e.g. in (CH 3 )3SnN(CH 3 ) 2 167 k J m o l - 1 ) .
Thus,
other
cyclic
derivatives
should
be
easy
available f r o m the reaction o f tin-nitrogen
com-
+ s
(CH 3 ) 3 Sn-N=S = N"Sn(CH 3 ) 3 + S
— •
S
CH3X
CH
p o u n d s with inorganic halides. I t should be added
\
/
+
(CH 3 ) 4 Sii
Sn
that in addition the formation o f a tin-halogen b o n d
is f a v o u r e d 2 .
The intermediates, sulfur and the tin substituted
sulfur diimide, (CH 3 ) 3 S n - N = S = N - S n (CH 3 ) 3 , might
* Paper, presented at the 1. International Symposium
on Inorganic Heteroevcles, Besangon (France), June
16-19, 1975.
Requests for reprints should be sent to Prof. Dr.
H. W . ROESKY, Anorganisch-chemisches Institut I der
Universität, Niederurseier Hang, D-6000
Frankfurt
a.M.
be obtained before heating the reaction mixture.
The
structure
of
the
cyclic
tin
compound
(CH3)2SnS2N2 has been determined 5 , the moleculc
existed of one four-membered and t w o
five-mem-
bered rings and the coordination number at the tin ifc
five as shown below. T h e molecule has Ci s y m m e t r y
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H. W . R O E S K Y • P R E P A R A T I O N A N D R E A C T I O N S OF S U L F U R - N I T R O G E N R I N G SYSTEMS
681
The five-membered sulfur-nitrogen o x i d e shown
above
is a red
oil at
room
temperature.
The
chemistry o f this c o m p o u n d 8 is essentially that
associated with the SO group, which undergoes a
number of the normal reactions of organic sulfur
oxides.
S = NSO,CF, + SO,
^S=0 + CF,S0,N=S=0
The molecule is also a dimer in solution but
monomeric in the gas phase. Another interesting
feature o f the structure is, that the molecule has
nearly a planar f o r m in the solid state. All the S - N
bonds are o f different length, the N - S - N and S - N - S
b o n d angles being 116.8° a n d 118.1°, respectively.
The b o n d lengths are intermediate between that
expected for a single (1.74 Ä ) and a double b o n d
(1.54 Ä). Comparing the S n - S - N angle o f 103.2°
with the N - S - N angle o f 116.8° a significantly
difference is observed, w h i c h is caused b y different
electron density. This illustrates that it is t o some
extent justified t o assign a f o r m a l o x i d a t i o n number
of + 2 f o r the sulfur b o n d e d t o tin and a formal
oxidation number of -j- 4 f o r the sulfur a t o m located
between the t w o nitrogen atoms. R e c e n t work has
shown that COF2 6 or SOF2 7 react at r o o m t e m perature with the tin c o m p o u n d under insertion and
Elimination o f dimethyltindifluoride.
s
+
+
COF,
S=NSO,F + SO,
"S=0 + FS0,N = S = 0
S = N-S-CF
22
11 ' 3 + C0
o
S=0 + CF,SO,NCO
Iminosulfur oxides and isocyanates react under
evolution of SO2 and CO2 respectively. The structure
o f the fluorosulfonyl derivative has been determined
b y X - r a y analysis 5 .
(CH3)2SnF2
o=c
4 OSO 119,9'
< NSF 101,0'
CHj.
CH3'
S +
S + SOF,
(CH3)2SnF2
0=SV
The interesting feature o f this structure is, that
the
exocyclic
N-S
bond
adjacent
t o the five
membered ring with a b o n d length o f 1.603 Ä is
greater than the O 2 S - N b o n d with distance
of
1.586 Ä .
The c y c l i c ketone is the first representative of a
These structural data confirm that the c o m p o u n d
aew class o f c o m p o u n d s t h a t have b e c o m e readily
is partly ionic and might be assumed having an
iccessible b y this method. COCI2 reacts similarly,
intermediate between the covalent and ionic f o r m
>ut separation o f the k e t o n e f r o m the dimethyl-
shown below.
indichloride proves difficult. T h e use o f fluoro
lerivatives is favoured b y f o r m i n g solid non-volatile
in-fluorides. T h e ketone is a y e l l o w
"S—NSO 2 F
crystalline
•ompound with m . p . 40.5 °C and it can be sublimed
n v a c u u m at r o o m temperature.
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H. W. R O E S K Y • PREPARATION AND REACTIONS OF SULFUR-NITROGEN RING SYSTEMS 68
B y using the well-known compound S3N2CI2 as a
starting material and nitrogen-tin derivatives we
were able to isolate bicyclic compounds 9 - 1 0 .
F
4
F F
X
I I A
/I
N
F
.P.
F'
\/
FJ
\/
F
*
V
+ 2(CH 3 ) 3 SnCI
.
. + S3N2CI2Sn(CH3)3
F F
S
N ' S
FJ
l/N
/ "\
2
\
F N
C—N=
V
/
the S - S distance is considerably longer 2.200 Ä than
in the cation 2.136 A. The electron density is
apparently much higher. A further point of interest
is, that the 6 ^-electron S2N2 part is not substantially
influenced. It was confirmed b y calculations on
S3N2CI4" that the ring may formally be regarded as
a pseudo-aromatic 6 .T-electron system 13 . Many
compounds with S - N bonds may, of course, be
synthesized from silicon-nitrogen derivatives. Typical of these is ( C H 3 ) 3 S i - N = S = N - S i ( C H 3 ) 3 . On reaction with CH3SiCl3 and the corresponding tin derivative the bicyclic silicon-sulfur-nitrogen compound
is formed 1 4 .
The question however, whether isomer 1 or 2 is
formed has been established by X - r a y analysis 11 . It
is found that the formation of the five-membered
ring is favoured. B y comparing the data of the
S3N2C1+ c a t i o n 1 2 wdth the N-S3N2 part of
P3N3F5NS3N2 we observe that,
The molecule has exact D3-symmetry 5 . A related
compound is obtained by using (CH3)2SiCl215. The
eight-membered ring was confirmed by X-ray
analysis 16 . Both compounds are sensitive to moisture
but can be sublimed without reduced pressure.
The products shown in the figures below resulted
from the reaction of ( C H 3 ) 3 S i - N = S = N - S i ( C H 3 ) E
with F S 0 2 - N = S = 0 in methylenechloride 17 .
P3N 3 F 5 -N-S 3 N 2
S,N +
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H. W . R O E S K Y • P R E P A R A T I O N A N D R E A C T I O N S OF S U L F U R - N I T R O G E N R I N G SYSTEMS
683
The ring is almost planar and the b o n d distance
across the ring are the same within experimental
error. The S - N b o n d lengths are in the range
1.543-1.580 Ä and are normal f o r a delocalized S - N
system, compared with the values o f 1.548-1.566 Ä
in the S4N 3 + ion.
S3N304
S4N4O2
T h e ionic species can be f o r m a l l y regarded as
being f o r m e d according t o the f o l l o w i n g equation:
2 S4N402 — S,N? + SjNjOf
T h e ionic c o m p o u n d crystallizes with a m o n o clinic cell, space g r o u p P21/C and f o u r units o f
S5N 5 + S 3 N 3 04- per cell. T h e shape o f the
S5N5+
cation observed, differs greatly f r o m the
heart-
shaped ion reported f o r SsNs+AlCU"
N
18 .
N
3
/'1,481
+
1
H. W.
2
H . W . ROESKY and B . KUHTZ, C h e m . B e r . , in press.
H . W . ROESKY and H . W I E Z E R , A n g e w . Chem. 8 5 ,
3
4
722 [1973].
H . W . ROESKY
3186 [1974].
[1974].
H.
WIEZER,
Chem.
Ber.
H . W . ROESKY and E.JANSSEN, Chem. Ber. 108, 2531
11
I. RAYMENT, unpublished results.
[1975].
13
6
H . W . ROESKY and E . WEHNER, A n g e w . C h e m . , in
press.
D.
CLARK,
B.
ADAMS, A .
J.
JBANISTER, D .
T.
and
14
H . W . ROESKY and H . WIEZER, A n g e w . Chem. 86,
15
H. W.
130 [1974],
ROESKY and H . WIEZER, Chemiker-Ztg.
661 [1973].
H . W . ROESKY and H . W I E Z E R , A n g e w . Chem. 8 7 ,
254 [1975].
H . W . ROESKY and G. HOLTSCHNEIDER, unpublished
16
H . W . R O E S K Y and E . JANSSEN, Chemiker-Ztg.
260 [1974].
18
98,
TEMPLETON,
D. KILCAST, Int. J. Sulfur Chem. 1, 143 [1971].
17
results.
9
A . ZALKIN, T . E . HOPKINS, and D . H .
Inorg. Chem. 5, 1767 [1966].
107,
B. KREBS, University of Bielefeld, unpublished
results.
8
10
12
and
5
7
S4N4O2 crystallizes in the non-centrosymmetric
space group A b m 2 with eight molecules per cell.
The molecule contains an eight-membered S4N4 ring
with b o t h oxygens attached t o the same sulfur
a t o m . This a t o m lies 1.52 Ä and the t w o adjacent
nitrogen atoms 0.41 Ä a b o v e the mean plane o f the
other ring atoms, which are coplanar t o within
0.014 Ä . T h e bonding could be described in terms o f
t w o sulfur diimide N S N fragments linked b y S and
SO2 bridges or, in view o f the approach t o planarity
o f the N 4 S 3 part o f the ring, as a 10 n delocalized
system linked into a ring b y the SO2 group.
I wish t o express m y thanks t o m y collaborators.
This work was supported b y F o n d s der Chemischen
Industrie and Deutsche Forschungsgemeinschaft.
1523
R O E S K Y , Chemiker-Ztg. 9 8 , 121
The S 3 N 3 04~ anion contains an S 3 N 3 ring with
t w o terminal oxygens on t w o o f the sulfur atoms.
W i t h i n experimental error, the i o n shows m s y m metry. The nitrogen a t o m situated between the t w o
SO2 groups is displaced b y 0.64 Ä out o f the mean
plane at the rest o f the ring as a consequence o f the
nearly tetrahedral angles at these t w o sulfur atoms.
T h e b o n d distances t o this nitrogen a t o m indicate
some multiple bonding and suggest that the
negative charge is delocalized over the S O 2 - N - S O 2
system. The b o n d distances in the diimide N - S - N
unit are very short, indicating substantial multiple
bonding in this part o f the ring where as the b o n d s
joining this unit t o the S O 2 - N - S O 2 portion o f the
ring lie within the range o f S - N single bonds.
97,
G . E R T L and J. WEISS, Z . Naturforsch. 29 b, 803 [1974].
H. W.
ROESKY, W .
GROOSE BÖWING, I.
RAYMENT,
and H . M . M . SHEARER, Chem. Commun. 1975, 735.
A . C. HAZELL and R . G . HAZELL, Acta Chem. Scand.
26, 1987 [1972].
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