Syntheses, structures and theoretical investigations of 1λ 4,3λ4,5λ 4-trithia-2,4,6,8,9-pentaazabicyclo[3.3.1]nona-1(9),2,3,5,7-pentaenes

Article abstract of DOI:10.1002/ejic.200300111

The syntheses of the title compounds RCN₅S₃ with electron-withdrawing aryl substituents [R = 2-FC₆H₄ (1m), 4-FC₆H₄ (1n), 2,6-F₂C₆H₃ (10), C₆F

Full text of DOI:10.1002/ejic.200300111

FULL PAPER
Syntheses, Structures and Theoretical Investigations of 1λ4,3λ4,5λ4-Trithia-
2,4,6,8,9-pentaazabicyclo[3.3.1]nona-1(9),2,3,5,7-pentaenes
Carsten Knapp,[a] Enno Lork,[a] Tobias Borrmann,[b] Wolf-Dieter Stohrer,[b] and
Rüdiger Mews*[a]
Keywords: Sulfur / Nitrogen / Fluorine / Solid-state structures / Quantum chemistry
The syntheses of the title compounds RCN5S3 with electron-
withdrawing aryl substituents [R = 2-FC6H4 (1m), 4-FC6H4
(1n), 2,6-F2C6H3 (1o), C6F5 (1p), 4-NCC6H4 (1q) and Cl3C
do not influence bonding within the bicycle. In the solid
state, two fundamentally different primary interactions of the
RCN5S3 molecules are observed; ‘‘stacking’’ and ‘‘dimeris-
(1r)] are described. The X-ray structures of 1n, 1o, 1q and 1r, ation’’, which can be rationalised by electrostatic interactions
together with those of Me2NCN5S3 (1b) and 4- between the CN5S3 units. However, secondary effects − the
CH3C6H4CN5S3 (1f), are reported. The experimentally deter- interactions between the R substituents − may be even
mined dependence of the bond lengths on the substituents R
within the bicyclic system RCN5S3 is well-reflected in the re-
sults of the theoretical calculations (RHF, MP2, B3LYP). The
bonding model developed shows that acceptor substituents
more dominant.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
Introduction
They are accessible via two different routes, either
from the reaction of 1,3-dichloro-1,3-dithiatriazines
(RCN)(NSCl)2 with Me3SiNSNSiMe3 (dithiatriazine route
A; Scheme 2), or from (NSCl)3 and tris(trimethylsilyl)amid-
ines RC(NSiMe3)[N(SiMe3)2] (amidine route B).
The
bicyclic
carbon-sulfur-nitrogen
heterocycles,
1λ4,3λ4,5λ4-trithia-2,4,6,8,9-pentaazabicyclo[3.3.1]nona-
1(9),2,3,5,7-pentaenes 1 (Scheme 1), are multifunctional
sulfur-nitrogen systems with a versatile chemistry.
Scheme 1. Note: The numbering in the top left represents the
IUPAC numbering scheme, the scheme below is that used consist-
ently in this article
Scheme 2
[a]
Institut für Anorganische und Physikalische Chemie der
Universität Bremen,
Postfach 330440, Leobener Straße, 28334 Bremen, Germany
Fax: (internat.) ϩ49-(0)421/218-4267
E-mail: mews@chemie.uni-bremen.de
The preparation of the chloro derivative, described by
route C,[5] is difficult to reproduce, but the compound is
also accessible via route A from (ClCN)(NSCl)2.[6] At-
tempts to prepare the corresponding fluoro derivative from
(FCN)(NSCl)2 resulted in a very unstable product.[6]
[b]
Institut für Organische Chemie der Universität Bremen,
Postfach 330440, Leobener Straße, 28334 Bremen, Germany
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
Eur. J. Inorg. Chem. 2003, 3211Ϫ3220
DOI: 10.1002/ejic.200300111
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3211

C. Knapp, E. Lork, T. Borrmann, W.-D. Stohrer, R. Mews
FULL PAPER
To date, the chemistry of these systems has not been well Results and Discussion
investigated. Based on MNDO calculations,[7] it has been
Syntheses of 1λ4,3λ4,5λ4-trithia-2,4,6,8,9-pentaazabicyclo-
[3.3.1]nona-1(9),2,3,5,7-pentaenes
proposed that the coordination chemistry of compounds 1
is varied. From the large number of chemically non-
equivalent donor and acceptor sites in 1, many interesting
and not readily predictable reaction possibilities are ex-
pected. To date, only the F3C derivative 1a has been intro-
duced as a ligand. [Ni(F3CCN5S3)2(OSO)2(FAsF5)2] and
[Ag(F3CCN5S3)(µ-F3CCN5S3)]2(AsF6)2 have been isolated
and characterised by X-ray crystallography.[7] The bicyclic
system undergoes nucleophilic attack with EPh3 (E ϭ P,
As), and 1e is transformed into the monocyclic eight-mem-
bered imino derivatives 2 (Scheme 3),[8] with weak transan-
nular SϪS bonds.
As expected, the bicyclic sulfur nitrogen systems 1mϪ1o
with partially fluorinated aryl substituents are readily pre-
pared by the amidine route B from silylated amidines and
trithiazyl trichloride. This route can also be used for the
preparation of the trifluoromethyl-substituted derivative 1a
(Scheme 5). Thus, 1a is more-readily accessible than pre-
viously reported.[1] It is not possible to use route B for the
preparation of derivatives with stronger electron-with-
drawing aryl groups (e.g. C6F5, 4-NCC6H4), since the corre-
sponding N,N,NЈ-tris(trimethylsilyl)amidines cannot be pre-
pared by silylation of lithium N,NЈ-bis(trimethylsilyl)amid-
ines with Me3SiCl. Their reactivity is greatly reduced due
to the electron-withdrawing groups.[15,16] In this case, the
corresponding lithium N,NЈ-bis(trimethylsilyl)amidines are
directly reacted with (NSCl)3 in diethyl ether. Under these
conditions, 1p and 1q are also formed, but in lower yields.
The compounds were obtained in a pure crystalline state by
recrystallisation from acetonitrile.
Scheme 3
Under the conditions of both thermolysis and photoly-
sis,[9] it was recently found that the bicyclic sulfur-nitrogen
heterocycles 1 afford the corresponding 1,2,3,5-dithiadiazo-
lyl radicals, which are of high interest.[10]
The dependence of the reactivity on the substituent R is
documented in the reaction of 1a and 1eϪk with elemental
chlorine. The aryl derivatives 1eϪk are readily degraded to
dithiatriazines 3eϪk (Scheme 4),[3,4] while the trifluorome-
thyl derivative 1a is not attacked under similar con-
ditions.[11,12]
Scheme 5
Compounds 1 can be stored at room temperature in an
inert atmosphere and do not decompose. The bicyclic sulfur
nitrogen framework undergoes chemical, photochemical or
thermal decomposition (partial or complete). In moist air,
most of the bicycles are transformed into a white solid
within a few hours or days. Even PhCN5S3, described in
the literature as air-stable,[3] will slowly decompose under
these conditions. Complete hydrolysis occurs according to
Scheme 6:
Scheme 4
From the structural and theoretical investigations we en-
deavoured to explain the different stabilities. Furthermore,
these theoretical investigations should allow us to predict
the reactivities and the properties of 1, based on the nature
of the substituent.
The X-ray structures of 1a,[1] 1d,[3,13] 1e[14] and 1l[5] have
been described previously. A preliminary theoretical dis-
cussion of the bonding properties based on MNDO calcu-
lations was reported earlier by our group.[1] In this paper,
the synthesis of compounds with electron-withdrawing sub-
stituents [RCN5S3: R ϭ 2-FC6H4 (1m), 4-FC6H4 (1n), 2,6-
F2C6H3 (1o), C6F5 (1p), 4-NCC6H4 (1q) and Cl3C (1r)], for
Scheme 6
The products from the direct complete hydrolysis in mo-
which an increased stability is expected, are reported. The ist CH2Cl2, detected by mass spectrometry (FAB) and
X-ray structures of selected compounds (1b, 1f, 1n, 1o, 1q chemical analysis, are the corresponding amidinium ions
and 1r) have been determined. The experimental results are and the NH4ϩ, sulfate and thiosulfate ions; only small
compared with the results of the theoretical calculations.
amounts of the sulfite ion are detected.
3212
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1λ4,3λ4,5λ4-Trithia-2,4,6,8,9-pentaazabicyclo[3.3.1]nona-1(9),2,3,5,7-pentaenes
FULL PAPER
The results of the mass spectrometric analysis of the pure been noted for electron-withdrawing groups (1g, 1h) vs.
bicyclic systems depend on the ionisation method applied. electron-donating groups (1f, 1i).[4]
With ionisation by EI, molecular ions are mostly detected,
Some years ago investigations on the thermal decompo-
but with low intensity. The peak representing the fragment sition of PhCN5S3 (1e) in acetonitrile solution were under-
[M Ϫ N3S]ϩ is always present. This corresponds to the taken; only benzonitrile and S4N4 were identified as the de-
stable 1,2,3,5-dithiadiazolylium cation bϩ (Scheme 7) The composition products.[17] More recent investigations of the
more gentle FI method also allows for the detection of mo- thermolysis of 1e in squalane by ESR spectroscopy have
lecular ions. Furthermore, the direct degradation products shown that the radicals b· and c· are formed as the de-
aϩ and bϩ are observed, together with the ions (cϩ, dϩ) composition products, in accord with the results of the mass
formed by recombination of the fragments.
spectrometric investigations mentioned before. Both rad-
icals are known from the literature and can be prepared by
straightforward methods.[18]
Structure Investigations
Single crystals of RCN5S3 [R ϭ Me2N (1b), 4-CH3C6H4
(1f), 4-FC6H4 (1n), 2,6-F2C6H3 (1o), 4-NCC6H4 (1q), and
Cl3C (1r)] were obtained by crystallisation from acetonitrile
Scheme 7
¯
at Ϫ40 °C. They crystallise in the triclinic space group P1
Chlorine cleaves the NSN bridge of the aryl-substituted with the exception of Cl3CCN5S3 (1r), which crystallises in
bicyclic systems, forming the 1,3-dichloro-1,3,2,4,6-dithia- the monoclinic space group P21/n with one molecule of
triazines.[3,4] In contrast to the aryl derivatives, the trifluoro- acetonitrile in the asymmetric unit. Crystal data and details
methyl derivative F3CCN5S3 (1a) is astonishingly stable and of the structure determinations are given in Table 1. Fig-
does not react with elemental chlorine or with ure 1 shows the structures and the numbering scheme of
SO2Cl2.[4,11,12] Attempts to obtain the corresponding dithia- 1o and 1q as representative examples. In these bicycles, the
triazines by degradation reactions of 1a with Br2 or different substituents only have a slight effect on the bond
(CF3)2NO also failed.[12] To date, no explanation for the lengths. The C1ϪN1 bond lengths (131.8Ϫ135.3 pm), the
unexpected stability could be given. In contrast to 1a, the N1ϪS1 bond lengths (158.3Ϫ164.0 pm) and the S1ϪN5
partially and fully fluorinated aryl derivatives 1o and 1p bond lengths (162.6Ϫ163.4 pm) lie in the range between
also react with chlorine in CCl4 (the reaction occurs within that of single and double bonds, while the S1ϪN2 bonds
a few minutes) to give the corresponding 1,3-dichloro- (172.3Ϫ174.8 pm) might be considered as single bonds and
1,3,2,4,6-dithiatriazines. An obvious dependence of the rate the N2ϪS2 bonds (154.0Ϫ155.2 pm) as double bonds. In
of chlorination on the substituents at the aryl groups has line with the mesomeric structures (Scheme 1), the bicyclic
Table 1. Crystal data and structure refinement data for 1b, 1f, 1n, 1o, 1q, and 1r
1b
1f
1n
1o
1q
1r
Empirical formula
Molecular mass
Crystal system
Space group
a, pm
b, pm
c, pm
α, deg
β,deg
γ, deg
V, nm3
Z
Dcalcd.., Mg/m3
Crystal size
θ range
C3H6N6S3
222.32
triclinic
¯
P1
625.90(10)
754.30(10)
916.2(2)
89.710(10)
80.26(2)
76.540(10)
0.41434(12)
2
C8H7N5S3
269.37
triclinic
¯
P1
594.90(10)
736.90(10)
1294.1(2)
78.850(10)
84.540(10)
73.640(10)
0.53357(14)
2
C7H4FN5S3
273.33
triclinic
¯
P1
594.7(2)
746.3(2)
1172.4(3)
101.53(3)
90.31(3)
105.95(2)
0.4892(2)
2
C7H3F2N5S3
291.32
triclinic
¯
P1
603.70(10)
770.90(10)
1147.80(10)
91.460(10)
90.350(10)
107.000(10)
0.51062(4)
2
C8H4N6S3
280.35
triclinic
¯
P1
476.60(10)
1082.9(5)
1159.3(4)
64.53(2)
87.97(2)
78.63(3)
0.5288(3)
2
C4H3Cl3N6S3
337.65
monoclinic
P21/n
592.50(10)
2916.5(3)
693.10(10)
90
92.500(10)
90
1.1966(3)
4
1.874
1.782
1.677
1.856
1.895
1.761
0.60 ϫ 0.40 ϫ 0.30 0.70 ϫ 0.60 ϫ 0.10 0.70 ϫ 0.50 ϫ 0.20 0.60 ϫ 0.40 ϫ 0.20 0.40 ϫ 0.30 ϫ 0.20 0.60 ϫ 0.40 ϫ 0.30
2.78Ϫ27.50
2.93Ϫ27.49
4994
2.90Ϫ27.50
4551
2.76Ϫ27.50
4704
3.45Ϫ23.50
2997
2.79Ϫ26.50
3394
Reflections collected 2227
Independent
reflections
1715
2460
2247
2327
1494
2488
Absorption
Ϫ
Ϫ
Ϫ
Ϫ
DIFABS
Ϫ
correction
Goodness-of-fit
Final R indices R1,
wR2
1.079
0.0359, 0.1006
1.074
0.0267, 0.0749
1.117
0.0261, 0.0744
1.103
0.0262, 0.0726
1.044
0.0656, 0.1578
1.062
0.0490, 0.1213
R indices (all data)
0.0375, 0.1019
0.0285, 0.0768
0.0276, 0.0760
0.0280, 0.0739
0.1043, 0.1802
0.0735, 0.1307
Eur. J. Inorg. Chem. 2003, 3211Ϫ3220
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3213

C. Knapp, E. Lork, T. Borrmann, W.-D. Stohrer, R. Mews
FULL PAPER
lengths. The C1ϪN1 bond length is increased by approxi-
mately 2 pm by electron-donating substituents (R ϭ
Me2N), and shortened by approximately 1.5 pm by elec-
tron-accepting substituents (R ϭ CF3), relative to the
weakly interacting phenyl group. The neighbouring N1ϪS1
bonds show the reverse effect. The effects on the other
bonds in the system, except on the S1ϪN2 bond, are within
experimental error. Directly bonded amino groups signifi-
cantly increase this bond length when compared with the
directly bonded electron-withdrawing groups and the aryl
substituents.
The change in the C1ϪN1 bond lengths is accompanied
by a change in the NCN angle: 127Ϫ128° for compounds
with donor substituents, around 130° for the aryl deriva-
tives, and up to 134Ϫ135° for the acceptor-substituted bi-
cycles.
In the aryl derivatives the twist angle τ between the aro-
matic phenyl ring and the plane of the five atoms (C1, N1,
N4, S1, S3) in the heterocycle is 26Ϫ29° for 1e, 1f and 1n,
i.e. the 6π-aromatic and the delocalised sulfur-nitrogen sys-
tems are not coplanar. However, in 1q, which has a strongly
electron-accepting nitrile group in the para position, the
two rings are virtually coplanar (τ ϭ 5.2°). However, this
does not lead to an apparent shortening of the exocyclic
CϪC1 bond. In 1o, the phenyl ring is 50.1° out of the plane
formed by the five atoms of the heterocycle, because of the
repulsive interactions between the fluorine atoms in the or-
tho-positions and the nitrogen atoms N1 and N4.
Figure 1. Crystal structures and numbering scheme of 1o and 1q
framework is best described as a dithiatriazine bridged by
a sulfur diimide group.
Closer examination of the bonding parameters shows the
effect of the substituents. The ten bicycles described in
Table 2 can be divided into three groups. Strong donors or
strong acceptors bonded directly to the bicycles each form
one group. The third group consists of all aryl-substituted
bicycles, the bond lengths of which are independent of the
Solid-State Packing
In the crystal, the packing of the molecules varies. Two
substituents at the aryl ring (they are equal within the range completely different arrangements of the bicycles are ob-
of standard deviations). served that can be described as ‘‘stacking’’ or ‘‘dimerisa-
The difference between the three different groups is par- tion’’. Stacking is found for the bicycles with R ϭ Cl (1l),
ticularly apparent in the C1ϪN1 and the N1ϪS1 bond F3C (1a) and 4-NCC6H4 (1q); a related structure is shown
Table 2. Selected bond lengths (pm) and angles (deg) for the bicyclic molecules RCN5S3
R
RϪC1
C1ϪN1
C1ϪN4
N1ϪS1
N4ϪS3
S1ϪN5
S3ϪN5
S1ϪN2
S3ϪN3
N2ϪS2
N3ϪS2
NCN
τ
ref.
[1]
F3C (1a)
152.4(4)
153.9(5)
175.1(2)
147.6(10)
149.7(2)
148.7(2)
148.5(3)
148.82(19)
134.6(3)
134.1(4)
131.6(3)
132.5(3)
131.6(5)
131.7(5)
132.0(2)
131.9(2)
132.5(9)
135.0(9)
133.3(2)
133.4(2)
133.8(2)
134.0(2)
133.9(3)
133.3(3)
134.04(19)
134.17(18)
135.2(3)
135.2(3)
135.0(5)
135.5(4)
163.1(2)
163.0(2)
163.7(3)
164.5(3)
163.3(2)
163.2(2)
162.0(6)
161.3(6)
162.76(14)
163.07(14)
162.39(14)
162.36(14)
162.1(2)
162.7(2)
163.3(2)
162.9(4)
162.9(4)
163.4(2)
172.3(2)
172.7(2)
172.6(3)
172.4(3)
173.1(2)
154.4(2)
154.6(2)
154.1(3)
155.0(4)
155.0(2)
134.1(2)
Ϫ
Cl3C (1r)
133.9(4)
Ϫ
this work
[5]
Cl (1l)
135.2(3)
Ϫ
4-NCC6H4 (1q)
2,6-F2C6H3 (1o)
4-FC6H4 (1n)
C6H5 (1e)
163.0(6)
162.1(7)
163.37(14)
163.02(14)
163.15(14)
163.38(14)
162.9(2)
173.9(7)
171.6(6)
172.97(16)
172.33(16)
173.49(16)
172.99(16)
172.8(2)
152.5(7)
155.8(6)
155.02(15)
155.41(15)
155.09(15)
155.23(15)
154.7(2)
129.2(7)
5.2
50.1
28.4
26.6
27.2
Ϫ
this work
this work
131.91(15)
133.35(15)
129.8(2)
this work
[3,13]
162.1(2)
163.0(2)
172.8(2)
154.6(2)
4-H3CC6H4 (1f)
Me2N (1b)
iPr2N (1d)
162.65(13)
162.62(13)
159.69(18)
160.06(19)
158.8(3)
163.22(13)
163.52(13)
163.51(19)
163.1(2)
163.3(3)
162.0(4)
173.50(14)
173.23(15)
175.45(19)
174.2(2)
174.5(3)
175.0(3)
154.93(14)
155.32(14)
154.66(19)
155.3(2)
153.6(3)
154.3(3)
130.36(14)
128.67(19)
127.0(3)
this work
this work
[2]
Ϫ
157.7(3)
3214
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1λ4,3λ4,5λ4-Trithia-2,4,6,8,9-pentaazabicyclo[3.3.1]nona-1(9),2,3,5,7-pentaenes
FULL PAPER
by (1d; R ϭ iPr2N). The sulfur-nitrogen rings fit into one (1o 291.5Ϫ11n 296.4 pm), and is thus shorter than the sum
another like stacked crates. Most of the aryl-substituted bi- of the van der Waals radii (335 pm).
cycles [R ϭ 4-H3CC6H4 (1f), 4-FC6H4 (1n), 2,6-F2C6H3
Figures 4Ϫ6 present crystal packing diagrams that show
(1o)] and the dimethylamino derivative (1b) form centro- the different arrangements of the bicycles in the crystal.
symmetric dimers. The structure of Cl3CCN5S3 (1r), which Figure 4 shows details of the crystal lattice of 1q, which is
crystallises with one equivalent of acetonitrile, is different representative of the stacking arrangement. The structures
and cannot be assigned to either of these two types.
of 1n (Figure 5) and 1e (Figure 6) show that the arrange-
The stacking of the bicycles is represented by 1q in Fig- ment in the crystal is dependent on the substituents at the
ure 2. Each heterocycle has one NδϪ···Sδϩ and one bicycles. The partially fluorinated aryl substituents form ad-
NδϪ···Cδϩ interaction with the molecule above. The ditional weak H-F interactions with neighbouring mol-
NδϪ···Sδϩ interacting distance between the bridging nitro- ecules. For example, in 1n (Figure 5), this leads to a head-
gen atom and the sulfur atom of the diimide bridge is head/tail-tail arrangement of the molecules, thus forming a
around 300Ϫ310 pm (1q 299.2, 1l 304.5, 1a 311.8 pm), de- chain. The offset parallel chains form layers. In the phenyl
pending on the substituent at the bicycle, and thereby lies derivative (1e), an arrangement (Figure 6) which resembles
within the sum of the van der Waals radii (335 pm). The a fishbone pattern is observed.
NδϪ···Sδϩ distance in 1d is significantly longer (327.4 pm),
which can be attributed to the repulsive steric effect of the
large isopropylamino groups. The same effect is also ob-
served for the NδϪ···Cδϩ distance between the bridging ni-
trogen atom and the carbon atom of the heterocycle. This
distance is more than 100 pm longer for 1d (438.8 pm) than
for the other three bicycles (around 315 pm). This is barely
within the sum of the van der Waals radii (320Ϫ325 pm).
The average distance between the planes through the paral-
lel phenyl rings is approximately 350 pm for 1q.
Figure 4. Crystal packing diagram of 1q
Theoretical Calculations
Theoretical investigations were undertaken with the goal
of finding explanations for the different stabilities of this
bicyclic system with respect to the substituents, and for the
different arrangements in the solid state. In Table 3, exper-
imental bond lengths and bond angles for 1a (R ϭ CF3),
1q (R ϭ 4-NCC6H4), 1e (R ϭ C6H5) and 1b (R ϭ Me2N),
representative examples for the different types of structures,
are compared with the results of the RHF, MP2 and B3LYP
calculations. As discussed previously, this bicyclic system is
best described as a six-membered dithiatriazine with two
sulfur atoms bridged by a sulfur diimide group. The exper-
Figure 2. Stacking of 1q in the crystal
In this case, ‘‘dimerisation’’ implies that two molecules imental bond lengths within the dithiatriazine fragment are
are arranged with their heterocyclic heads facing each other in reasonable agreement with all three methods, the best fit
(represented in Figure 3). The second molecule is rotated is found with the RHF calculations. The S1ϪN2 distances
by 180° with respect to the first, so that two NδϪ···Sδϩ inter- between the sulfur of the dithiatriazine fragment and the
actions can be formed. The shortest distances between the sulfur diimide group, obtained by the RHF method, are
molecules, independent of the substituent, is around 295 pm slightly shorter than those determined experimentally. The
Figure 3. Centrosymmetric Dimer of 1n
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C. Knapp, E. Lork, T. Borrmann, W.-D. Stohrer, R. Mews
FULL PAPER
Figure 5. Crystal packing diagram of 1n
distances resulting from the MP2 and B3LYP calculations
are much larger. Similar results were obtained for the axial
SϪF distances in the related difluorodithiatriazines
RCN3S2F2 (R ϭ F, CF3). The RHF calculated distances
are shorter and the MP2 and B3LYP calculated distances
are much longer than those determined experimentally. The
distances within the dithiatriazine are also well-reflected by
all three methods.[19] The S2ϪN2 distances in the sulfurdi-
imide groups in 1, calculated by the MP2 method, show the
largest deviations (too long). Once again, the RHF calcu-
lated bond lengths are too short and those calculated by
the B3LYP method are too long. Similar results have re-
cently been obtained from the calculations of the molecular
geometries of thioaminyl radicals.[20]
On the other hand, inspection of Table 3 shows that the
experimentally determined influence of the different sub-
stituents on the bond lengths and on the NCN bond angle
Figure 6. Crystal packing diagram of 1e
Table 3. Averaged calculated (RHF/6Ϫ311G*, MP2/6Ϫ311G*, B3LYP/6Ϫ311G*) bond lengths and angles of 1a, 1b, 1e, and 1q
R
Method
C1ϪN1
(pm)
N1ϪS1
(pm)
S1ϪN5
(pm)
S1ϪN2
(pm)
N2ϪS2
(pm)
RϪC1
(pm)
τ (deg)
NϪCϪN
(deg)
NIMAG[a]
F3C (1a)
Exp.
RHF
MP2
B3LYP
RHF
MP2
B3LYP
Exp.
RHF
MP2
B3LYP
Exp.
RHF
MP2
B3LYP
Exp.
132.1
130.5
133.1
132.4
131.3
133.7
133.0
133.8
131.9
134.1
133.8
133.6
132.2
134.2
134.1
135.2
133.6
135.5
135.4
163.1
162.4
164.0
165.4
162.4
163.8
165.5
161.7
161.5
163.1
164.2
162.1
161.1
162.7
163.8
159.8
159.6
161.1
162.0
163.0
161.2
163.5
165.3
161.5
164.1
165.8
162.6
161.2
163.6
165.3
163.0
161.3
163.6
165.5
163.3
161.4
163.7
165.6
172.5
170.8
177.4
178.7
171.1
178.2
179.1
172.8
171.3
178.3
179.5
172.8
171.6
178.7
180.1
174.3
172.1
179.6
180.9
154.5
151.3
159.5
156.9
151.3
159.8
157.0
154.1
151.2
159.4
156.8
154.7
151.2
159.5
156.8
155.0
151.2
159.5
156.8
152.4(4)
153.2
153.0
154.2
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
5.2
0
0
0
26.6
0
0
134.1(2)
133.3
134.5
133.8
133.0
133.8
133.8
129.2(7)
130.0
131.2
130.3
129.8(2)
129.5
130.7
129.7
128.67(19)
128.5
130.0
Ϫ
0
Ϫ
0
0
Ϫ
0
Ϫ
0
Ϫ
0
Ϫ
0
Ϫ
0
Ϫ
0
Ϫ
H
Ϫ
Ϫ
4-NCC6H4 (1q)
147.6(10)
149.7
149.0
149.4
148.6(3)
149.2
148.9
149.0
134.6(3)
134.3
135.7
135.9
C6H5 (1e)
Me2N (1b)
0
Ϫ
Ϫ
Ϫ
Ϫ
RHF
MP2
B3LYP
128.7
0
[a]
Number of imaginary frequencies.
3216
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2003, 3211Ϫ3220

1λ4,3λ4,5λ4-Trithia-2,4,6,8,9-pentaazabicyclo[3.3.1]nona-1(9),2,3,5,7-pentaenes
FULL PAPER
is quite well-reflected by all three methods. Compared with utilised recently to rationalise the solid state packing of
the CF3 derivative 1a, C1ϪN1 increases by 1Ϫ1.5 pm in other SN systems,[22] a different picture is obtained. In Fig-
the aryl derivatives 1q, 1e, and to 2.5Ϫ3 pm in the Me2N ure 8, representative examples for stacking (R ϭ CF3, Fig-
compound 1b; S1ϪN1 decreases by 1Ϫ1.5 pm in 1q, 1e and ure 8a) and dimerisation (R ϭ NMe2, Figure 8b) are
to 2.8Ϫ3.4 pm in 1b. S1ϪN5 and the diimide bond N2ϪS2 shown. Positive electrostatic potential (ESP; blue) and
are not affected. According to the experiments, a marginal negative ESP (red) fit perfectly together in the dimer of 1b
lengthening of the axial S1ϪN2 bond is observed when go- (R ϭ NMe2). For R ϭ CF3, the ESP’s at S2 and N5 are
ing from 1b to 1q and 1e, the calculations show a slightly not very pronounced. Furthermore, the negative potentials
larger effect. A stronger influence on the lengthening of this of N5 and C3 are lower than in the NMe2 derivative, there-
bond is shown by experiment and by the calculations for fore ‘‘stacking’’ is less hindered by repulsive interactions.
1b, but this difference can hardly account for the different
Table 4. Calculated Mulliken and NBO charges (RHF/6Ϫ311G*)
of 1a, 1b, 1e, and 1q
stabilities of 1q, 1e, 1b compared with 1a. The larger in-
crease in the NCN angle in 1b relative to 1q, 1e is also
shown by experiment and by calculations.
R
Method
C1
N1
S1
N5
N2
S2
The influence of the substituents can already be ex-
plained in terms of the (extended) frontier orbital model.
The energetically highest occupied donor orbitals of the
substituents interact with the energetically lowest unoccu-
pied acceptor orbital of the bicycles with the same sym-
metry, as shown in Figure 7. By this, the a priori empty
(unoccupied) acceptor orbital with antibonding character
in the CN and bonding character in the SN region is partly
populated, thus explaining the lengthening of the CϪN and
the shortening of the SϪN bonds. These results are in per-
fect agreement with our MNDO calculations reported ear-
lier.[1]
F3C (1a)
Mulliken 0.244 Ϫ0.608 0.998 Ϫ0.793 Ϫ0.710 1.006
NBO 0.519 Ϫ0.899 1.546 Ϫ1.185 Ϫ1.070 1.466
4-NCC6H4 Mulliken 0.555 Ϫ0.672 0.992 Ϫ0.793 Ϫ0.714 0.994
(1q)
NBO
Mulliken 0.561 Ϫ0.672 0.985 Ϫ0.797 Ϫ0.716 0.985
NBO 0.636 Ϫ0.947 1.547 Ϫ1.192 Ϫ1.072 1.450
Me2N (1b) Mulliken 0.737 Ϫ0.708 0.978 Ϫ0.807 Ϫ0.721 0.972
NBO 0.821 Ϫ0.998 1.555 Ϫ1.199 Ϫ1.083 1.439
0.626 Ϫ0.941 1.550 Ϫ1.189 Ϫ1.074 1.457
C6H5 (1e)
Figure 7. Interaction of the energetically highest occupied orbitals
of the donor D with the energetically lowest unoccupied acceptor
orbital with the same symmetry
Compared to the experimentally yet unknown hydrogen
derivative included in the calculations in Table 3, acceptor
substituents have no effect on the bond lengths. This is be-
cause the energetically highest occupied orbital in the bicy-
cle with the appropriate symmetry is too low in energy for
significant interaction with an empty acceptor orbital. The
analysis of the orbitals with different model acceptors also
confirms this. The acceptor orbital only shows negligible
mixing with other orbitals. This also explains why the phe-
nyl group acts as a donor only.
Figure 8. MEP (mapped electrostatic potential) of representative
examples for stacking (R ϭ CF3) and for dimerisation (R ϭ NMe2)
Another aim of the quantum chemical calculations was
to find an explanation for the different crystallisation pat-
tern: ‘‘stacking’’ and ‘‘dimerisation’’, and how this is depen-
dent upon the substituents R.
Conclusions
Several new aryl 1λ4,3λ4,5λ4-trithia-2,4,6,8,9-pentaaza-
The Mulliken and NBO charges (Table 4) for the atoms bicyclo[3.3.1]nona-1(9),2,3,5,7-pentaenes RCN5S3 were pre-
S2 and N5 at which the dimerisation occurs show virtually pared by the amidine route from (NSCl)3 and ArC(NSi-
no dependency on the group R, therefore no correlation Me3)N(SiMe3)2. When the persilylated amidines cannot be
between the crystallisation pattern and the type of substitu- obtained from lithium-amidinates RC(NSiMe3)2Li (R ϭ
ent can be observed. However, when we consider the MEP C6F5, 4-NCC6H4) and Me3SiCl, due to the decreased nucle-
(mapped electrostatic potential),[21] which has also been ophilicity of the amidinate, the amidinates can be used di-
Eur. J. Inorg. Chem. 2003, 3211Ϫ3220
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3217

C. Knapp, E. Lork, T. Borrmann, W.-D. Stohrer, R. Mews
FULL PAPER
Paragon 500 FT-IR instrument. Mass spectra were measured on a
Finnigan MAT 8200, using the field ionisation (FI) technique. The
high-resolution mass spectra were obtained by using the peak
matching method (chemical ionisation neg.). Melting points were
obtained on a Gallenkamp melting point apparatus and are uncor-
rected.
rectly as starting materials. Contrary to our expectations,
the introduction of electron-withdrawing aryl groups does
not increase the stability of the RCN5S3 system.
The results of X-ray structure investigations and the
theoretical calculations are in good agreement. The influ-
ence of the substituents on bonding is readily understood
from the extended frontier orbital model. Compared with Preparation of F3CCN5S3 (1a): F3CC(NSiMe3)[N(SiMe3)2] (13.7 g,
42 mmol) in 50 mL of dichloromethane was added dropwise to tri-
thiazyl trichloride (10.0 g, 41 mmol) in 100 mL of dichloromethane
at 0 °C. The solution became dark red. The solvent and all volatile
products were removed and the remaining residue was dissolved in
100 mL of acetonitrile and the solution was filtered. On storage at
Ϫ40 °C, yellow crystals were obtained (6.35 g, 26 mmol, 63%
yield). The spectroscopic data are in accordance with literature
data.[1] MS-FI: m/z ϭ 247 (100) [Mϩ]. MS-HR: found 246.92615,
calcd. 246.92679.
the parent hydrogen derivative, acceptor substituents have
no effect, since the -CN5S3 HOMO of appropriate sym-
metry is too low in energy for significant interaction. The
interaction of the donor orbitals with the LUMO of appro-
priate symmetry will increase the CϪN bond lengths and
decrease the lengths of the adjacent SϪN bonds because
the antibonding and bonding character in these regions is
increased. The influence on the other bonds is only mar-
ginal because of the nonbonding character of the LUMO
in these regions. The calculations show a slight increase of
the S1ϪN2 bond lengths when going from electron-with-
drawing to aryl to amino-substituted bicycles. The exper-
imentally observed significant lengthening of the S1ϪN2
bond in the amino derivatives is not reflected by the calcu-
lations.
Preparation of 2-FC6H4CN5S3 (1m): 2-FC6H4C (NSiMe3)-
[N(SiMe3)2] (14.5 g, 41 mmol) in 100 mL of acetonitrile was added
dropwise to trithiazyl trichloride (10.0 g, 41 mmol) in 100 mL of
acetonitrile. The solution became dark red and a precipitate
formed. The solvent and all volatile products were removed and
the remaining residue was dissolved in 150 mL of boiling aceto-
nitrile and the solution was filtered. On cooling to room tempera-
ture, yellow crystals were obtained (7.7 g, 28 mmol, 69% yield),
No explanation can be given for the unusual stability of
the CF3 derivative from the structural data and the theoreti- m.p. 111 °C. 1H NMR: δ ϭ Ϫ7.16 ppm (ddd, 3JH,F ϭ 11.3, 3JH,H ϭ
8.3, 4JH,H ϭ 1.0 Hz, 1 H, m-C6H4F), 7.25 (td, 3JH,H ϭ 7.5, 4JH,H ϭ
cal calculations (the chemistry of the CCl3 derivative was
3
3
1.0 Hz, 1 H, m-C6H4F), 7.50 (dddd, JH,H ϭ 8.3, JH,H ϭ 7.5,
not investigated). From the large negative charges at the
nitrogen centres (Table 4), the RCN5S3 derivatives are ex-
pected to act as multifunctional donor ligands. When going
from CF3 to aryl to Me2N, only the positive charges at C1
and the negative charges at N2 increase, the charges at the
other centres are not affected. Therefore, a priori the ligand
properties should not be dependent on the substituents R.
In the solid state, two fundamentally different packing
4JH,F ϭ 4.8, 4JH,H ϭ 2.0 Hz, 1 H, p-C6H4F), 7.91 (td, JH,H ϭ 7.5,
3
4JH,F ϭ 7.5, JH,H ϭ 2.0 Hz, 1 H, o-C6H4F ppm. 13C{1H} NMR:
4
2
δ ϭ 117.1 (d, JC,F ϭ 22 Hz, m-C6H4F), 124.1 (s, m-C6H4F), 125.4
(d, 2JC,F ϭ 8 Hz, ipso-C6H4F), 130.8 (s, o-C6H4F), 133.6 (d, 3JC,F ϭ
1
8 Hz, p-C6H4F), 161.1 (d, JC,F ϭ 259 Hz, o-C6H4F), 165.6 (d,
3JC,F ϭ 4 Hz, NCN) ppm. 19F NMR: δ ϭ Ϫ113.3 (ddd, JF,H
ϭ
3
4
11.3, JF,H ϭ 7.5, JF,H ϭ 4.8, 1F) ppm. IR: ν˜ ϭ 1508 w, 1485 m,
1451 m, 1410 m, 1342 s, 1263 w, 1226 m, 1154 m, 1101 m, 996 s,
patterns are observed for RCN5S3, stacking of the RCN5S3 927 m, 843 w, 822 w, 770 s, 745 s, 721 s, 685 w, 670 m, 574 s, 551
m, 504 s, 476 m cmϪ1. MS-FI: m/z ϭ 273 (48) [Mϩ]. MS-HR:
found 272.96192, calcd. 272.96130.
molecules and face-to-face dimerisation of the N3S3 subun-
its of the ϪCN5S3 bicycle. The dependence of the packing
pattern on the substituents is difficult to predict. Primary
electrostatic interactions are responsible for the different
Preparation of 4-FC6H4CN5S3 (1n): The procedure follows that of
1m. 4-FC6H4C(NSiMe3)[N(SiMe3)2] (14.5 g, 41 mmol) was reacted
packing as shown by the MEP in Figure 8, but they might
be dominated by steric requirements of the substituents R
and by interactions between the substituents.
with trithiazyl trichloride (10.0 g, 41 mmol). After recrystallisation
from CH3CN, 1n (7.8 g, 29 mmol, 71% yield) was obtained as or-
ange crystals, m.p. 132 °C. 1H NMR: δ ϭ 7.07Ϫ7.19 (m, 2 H,
C6H4F), 8.18Ϫ8.28 (m, 2 H, C6H4F) ppm. 13C{1H} NMR: δ ϭ
2
3
115.5 (d, JC,F ϭ 21 Hz, m-C6H4F), 129.9 (d, JC,F ϭ 9 Hz, o-
4
C6H4F), 132.4 (d, JC,F ϭ 2 Hz, ipso-C6H4F), 164.6 (s, NCN),
Experimental Section
1
166.1 (d, JC,F ϭ 237 Hz, p-C6H4F) ppm. 19F NMR: δ ϭ Ϫ107.2
(tt, 3JF,H ϭ 8.3, 4JF,H ϭ 5.5 Hz, 1F) ppm. IR: ν˜ ϭ 2932 w, 1594 m,
1503 m, 1422 s, 1360 m, 1339 s, 1296 w, 1225 m, 1152 m, 1093 w,
997 s, 967 sh, 926 w, 849 m, 829 w, 814 m, 776 s, 750 s, 718 s, 688
w, 668 m, 629 w, 597 w, 573 s, 516 w, 490 s, 480 m cmϪ1. MS-FI:
m/z ϭ 273 (100) [Mϩ]. MS-HR: found 272.96244, calcd. 272.96130.
Materials and Methods: All manipulations of air-sensitive materials
were performed under an inert atmosphere of dry nitrogen, with
the absence of oxygen and moisture. The fluorinated N,N,NЈ-tris-
(trimethylsilyl)amidines {R ϭ F3C,[15] R ϭ 4-FC6H4, 2-FC6H4,
2,6-F2C6H3[16]}, [(C6F5C(NSiMe3)2Li]2·OEt2,[16] [(Me3Si)2-
NLi·OEt2]2,[23] Cl3CCN(NSCl)2,[24] Me3SiNSNSiMe3,[25] RCN5S3 Preparation of 2,6-F2C6H3CN5S3 (1o): 2,6-F2C6H3C(NSiMe3)-
[R ϭ 4-H3CC6H4, 4-C6H5C6H4,[4] R ϭ Me2N[2]] and trithiazyl-
[N(SiMe3)2] (9.3 g, 25 mmol) was reacted with trithiazyl trichloride
were prepared according to published pro- (6.1 g, 25 mmol). After recrystallisation from boiling acetonitrile
[26]
trichloride (NSCl)3
cedures. Terephthalonitrile is a commercial compound. The sol-
vents were carefully dried and distilled prior to use. NMR spectra
were recorded on Bruker DPX 200 (1H, 19F) and on Bruker AM
360 NB (13C) spectrometers in [D1]chloroform. Chemical shifts are
given with respect to Me4Si. Infrared analyses were acquired as
thin Kel-F and Nujol films (with KBr cells), using a PerkinϪElmer
and storage at Ϫ40 °C, 1o (4.9 g, 17 mmol, 68% yield) was obtained
as yellow-brown crystals, m.p. 104 °C. 1H NMR: δ ϭ 6.92Ϫ7.04
(m, 2 H, m-C6F2H3), 7.32Ϫ7.43 (m, 1 H, p-C6F2H3) ppm. 13C{1H}
NMR: δ ϭ 111.9 (dd, 2JC,F ϭ 23, 4JC,F ϭ 2 Hz, m-C6F2H3), 111.9
2
3
(t, JC,F ϭ 13 Hz, ipso-C6F2H3), 131.8 (t, JC,F ϭ 10 Hz, p-
1
3
C6F2H3), 159.8 (dd, JC,F ϭ 254, JC,F ϭ 6 Hz, o-C6F2H3), 163.5
3218
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2003, 3211Ϫ3220

1λ4,3λ4,5λ4-Trithia-2,4,6,8,9-pentaazabicyclo[3.3.1]nona-1(9),2,3,5,7-pentaenes
FULL PAPER
3
4
(s, NCN) ppm. 19F NMR: δ ϭ Ϫ114.9 (dd, JF,H ϭ 7.8, JF,H
ϭ
with a graphite monochromator. The crystals were mounted using
6.2 Hz, 2F) ppm. IR: ν˜ ϭ 2926 w, 1622 m, 1591 m, 1566 w, 1472 Kel-F oil onto a thin glass fibre. Details of the data collection and
m, 1344 s, 1238 m, 1148 m, 1011 s, 966 sh, 929 w, 818 w, 792 m, refinement are given in Table 1. The programs SHELX-97[27] and
776 m, 752 s, 630 m, 690 w, 670 m, 576 s, 523 w, 503 sh, 489 s, 467 DIAMOND[28] were used. The structures were solved by direct
m cmϪ1. MS-FI: m/z ϭ 291 (45) [Mϩ]. MS-HR: found 290.95194, methods (SHELXS).[27] Subsequent least-squares refinement
calcd. 290.95187.
(SHELXL 97Ϫ2)[27] located the positions of the remaining atoms
in the electron density maps. Non-hydrogen atoms were refined an-
isotropically. Hydrogen atoms were placed in calculated positions
using a riding model and refined isotropically in blocks.
Preparation of C6F5CN5S3 (1p): [C6F5C(NSiMe3)2Li]2·OEt2 (7.1 g,
18 mmol) in 50 mL of diethyl ether was added dropwise to trithia-
zyl trichloride (4.6 g, 19 mmol) in 50 mL of diethyl ether. The solu-
tion became dark red. The solvent and all volatile products were
removed and the remaining residue was dissolved in 100 mL of
acetonitrile and the solution was filtered. On storage at Ϫ40 °C,
yellow-brown crystals were obtained (2.4 g, 7 mmol, 39% yield),
CCDC-205700 (1b) -205701 (1f) -205702 (1n) -205703 (1r) -205704
(1o) and -205705 (1q) contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge
CB2 1EZ, UK; Fax: (internat.) ϩ44-1223/336-033; E-mail:
deposit@ccdc.cam.ac.uk].
m.p. 97 °C. 13C{1H} NMR: δ ϭ 115.0 (t, JC,F ϭ 17 Hz, ipso-
C6F5), 138.7 (dm, JC,F ϭ 253 Hz, o-C6F5), 143.2 (dm, JC,F
2
1
1
ϭ
1
253 Hz, p-C6F5), 145.2 (dm, JC,F ϭ 247 Hz, m-C6F5), 162.1 (s,
NCN) ppm. 19F NMR: δ ϭ Ϫ145.5 (dddd, JFF ϭ Ϫ21.8, JFF
ϭ
ϭ
ϭ
3
4
Quantum Chemical Calculations: All ab initio calculations were per-
formed with the GAUSSIANЈ98 program package.[29] The mapped
electrostatic potential (MEP) representations are made with
MOLEKEL.[21]
4
5
3
Ϫ4.7, JFF ϭ 3.2, JFF ϭ 8.0 Hz, 2F, o-F), Ϫ154.9 (tt, JFF
4
3
3
Ϫ20.2, JFF ϭ 3.2, 1F, p-F), Ϫ164.3 (dddd, JFF ϭ Ϫ21.8, JFF
4
5
Ϫ20.2, JFF ϭ Ϫ0.8, JFF ϭ 8.0 Hz, 2F, m-F) ppm. IR: ν˜ ϭ 1656
w, 1524 m,. 1504 s, 1427 sh, 1402 s, 1360 s, 1278 m, 1200 s, 1171
m, 1151 m, 1126 s, 1040 w, 1016 w, 986 m, 972 s, 901 m, 812 m,
761 sh, 722 s, 703 sh, 656 w, 626 w, 598 w, 570 w, 555 w, 531 m,
504 m, 473 m cmϪ1. MS-FI: m/z ϭ 345 (26) [Mϩ]. MS-HR: found
344.92149, calcd. 344.92361.
Acknowledgments
Financial Support by the FNK, Universität Bremen is gratefully
acknowledged.
Preparation of 4-NCC6H4CN5S3 (1q): A solution of lithium bis(tri-
methylsilyl)amide (3.9 g, 16 mmol) and terephthalonitrile (2.1 g,
16 mmol) in 150 mL of diethyl ether was added dropwise to trithia-
zyl trichloride (4.4 g) in 50 mL of diethyl ether at 0 °C. The solution
became brown. The solvent and all volatile products were removed
and the remaining residue was dissolved in 100 mL of dichloro-
methane and the solution was filtered. On storage at Ϫ40 °C, or-
ange crystals were obtained (1.4 g, 5 mmol, 31% yield), m.p. 158
[1]
R. Maggiulli, R. Mews, W.-D. Stohrer, M. Noltemeyer, G. M.
Sheldrick, Chem. Ber. 1988, 121, 1881Ϫ1889.
T. Chivers, J. F. Richardson, N. R. M. Smith, Inorg. Chem.
[2]
1986, 25, 272Ϫ275.
[3] [3a]
´
R. T. Boere, A. W. Cordes, R. T. Oakley, J. Chem. Soc.,
Chem. Commun. 1985, 929Ϫ930. [3b] R. T. Boere, A. W. Cordes,
´
R. T. Oakley, Acta Crystallogr., Sect. C 1985, 42, 1833Ϫ1834.
R. T. Boere, J. Fait, K. Larsen, J. Yip, Inorg. Chem. 1992, 31,
[4]
[5]
[6]
[7]
1
3
4
5
´
°C. H NMR: δ ϭ 7.75 (ddd, JH,H ϭ 8.3, JH,H ϭ 2.0, JH,H
ϭ
4
5
1.5 Hz, 2 H, C6H4), 8.33 (ddd,3JH,H ϭ 8.3, JH,H ϭ 2.0, JH,H
ϭ
1417Ϫ1423.
A. J. Banister, W. Clegg, I. B. Gorrell, Z. V. Hauptmann, R.
W. H. Small, J. Chem. Soc., Chem. Commun. 1987, 1611Ϫ1613.
S. J. Chen, Doctoral thesis, Universität Bremen, Germany,
1993.
1.5 Hz, 2 H, C6H4) ppm. 13C{1H} NMR: δ ϭ 116.9 (s, p-C6H4),
119.0 (s, NC), 128.9 (s, o-C6H4), 133.0 (s, m-C6H4), 141.2 (s, ipso-
C6H4), 165.4 (s, NCN) ppm. IR: ν˜ ϭ 2226 m, 1413 m, 1366 m,
1334 m, 1299 m, 1188 w, 1148 m, 1110 w, 1035 w, 1009 sh, 975 s,
921 w, 858 m, 836 w, 785 w, 768 sh, 750 m, 722 s, 692 m, 666 s,
642 sh, 561 m, 541 s, 506 m, 490 w, 467 m cmϪ1. MS-FI: m/z ϭ 280
(12) [Mϩ], 206 (NCC6H4CN2S2ϩ, 100). MS-HR: found 279.96632,
calcd. 279.96597.
R. Maggiulli, R. Mews, W.-D. Stohrer, M. Noltemeyer, Chem.
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R. T. Boere, A. W. Cordes, S. L. Craig, J. B. Graham, R.
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R. T. Boere, G. Ferguson, R. T. Oakley, Acta Crystallogr., Sect.
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´
R. T. Boere, A. W. Cordes, R. T.
C 1986, 42, 900Ϫ902.
Preparation of Cl3CCN5S3 (1r): Me3SiNSNSiMe3 (0.8 mL, 0.7 g,
3.5 mmol) in 10 mL of carbon tetrachloride was added dropwise to
Cl3CCN(NSCl)2 (0.85 g, 2.7 mmol) in 25 mL of carbon tetra-
chloride. After standing overnight, the solvent and all volatile prod-
ucts were removed and the remaining residue was dissolved in a
small amount of acetonitrile and the solution was filtered. On stor-
age at Ϫ40 °C and after drying under vacuum, yellow crystals of
1r·CH3CN (0.55 g, 1.9 mmol, 68% yield) were obtained, m.p. 102
°C. 13C NMR: δ ϭ 97.3 (s, CCl3), 168.4 (s, NCN) ppm. IR: ν˜ ϭ
1545 w, 1503 w, 1467 w, 1430 s, 1400 sh, 1362 m, 1292 s, 1265 sh,
1211 sh, 1202 m, 1171 w, 1151 m, 1127 w, 1028 m, 1004 sh, 987 m,
972 m, 946 sh, 916 sh, 872 sh, 862 m, 801 m, 758 m, 739 sh, 722 s,
Oakley, J. Am. Chem. Soc. 1987, 109, 7781Ϫ7785.
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R. T. Boere, R. T. Oakley, R. W. Reed, N. P. C. Westwood,
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A. W. Cordes, R. T. Oakley, R. T. Boere, Acta Crstallogr., Sect.
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702 w, 692 m, 660 m, 639 w, 567 m, 559 m, 506 s, 402 m cmϪ1
.
T. Chivers, F. Edelmann, J. F. Richardson, N. R. M. Smith, O.
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R. T. Boere, R. T. Oakley, M. Shevalier, J. Chem. Soc.,
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˚
on a Siemens P4 diffractometer using Mo-Kα (0.71073 A) radiation
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Received February 25, 2003
3220
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2003, 3211Ϫ3220