5,6-Diphenyl[1,3]dithiolo[4,5-6]-dithiine-2-thione

Full text of DOI:10.1107/s0108270101006679

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
determined and has been published (Kaynak et al., 2001). In
the light of this result, it was suggested that the reaction
proceeds via a radical mechanism, which led us to repeat the
reaction in the dark. Thus, the diphenyldithiine (VII) was
obtained in 65% yield.
ISSN 0108-2701
5,6-Diphenyl[1,3]dithiolo[4,5-b]-
dithiine-2-thione
a
a
b
È
È
F. Betul Kaynak, Suheyla Ozbey, * Turan Ozturk and
È
È
È
Erdal ErtaËsb
aDepartment of Engineering Physics, Hacettepe University, Beytepe 06532, Ankara,
Turkey, and bMarmara Research Center, Department of Chemistry, 41470 Gebze,
Kocaeli, Turkey
Correspondence e-mail: sozbey@hacettepe.edu.tr
Received 1 February 2001
Accepted 20 April 2001
In the title compound, C17H10S5, the dithiine ring adopts a
boat conformation while the dithiole ring has an envelope
conformation. The phenyl groups are planar and make
dihedral angles of 40.7 (2) and 59.8 (2)ꢁ with the best plane
of the thiine ring. The shortest intermolecular SÁ Á ÁS contact is
Ê
3.305 (2) A.
Comment
There has been wide interest in the introduction of increased
conjugation to bis(ethylenedithio)tetrathiafulvalene [BEDT±
TTF or ET, (I)], which is an electron-donating molecule. Its
radical cation salts show electrical conductivity and, in some
cases, superconductivity at lower temperatures (Williams et al.,
1985). Although the introduction of conjugation has been
achieved in the middle of the molecule (Bryce, 1995), there
are limited examples of the introduction of conjugation at the
peripheral ethylene groups (Inoue et al., 1986; Yamada et al.,
1996; Skabara et al., 1999). This is mainly due to the limited
availability of methodology in the literature.
In this context, attempts to synthesize a fully unsaturated
ET analogue with peripheral phenyl groups, (II), have so far
failed (Noh et al., 1996; Lee et al., 1998; Lee & Noh, 1998). On
the other hand, we recently reported a concise synthesis of 5,6-
diphenyl[1,3]dithiolo[4,5-b]dithiine-2-thione, (VII), and its
We report here the crystal structure of 5,6-diphenyl[1,3]-
dithiolo[4,5-b]dithiine-2-thione, (VII). The structure predicted
from chemical and spectral analysis is con®rmed. The mole-
cular structure is shown in Fig. 1. Structural results show that
the six-membered ring adopts the boat conformation having
spherical polar set values (Cremer & Pople, 1975) Q =
ꢁ
ꢁ
Ê
0.770 (3) A, ꢀ = 91.6 (3) and ' = 178.9 (3) . Atoms S4 and S5
are displaced from the C2/C3/C4/C5 mean plane by 0.697 (2)
Ê
and 0.636 (2) A, respectively. The dithiole ring fused to the
six-membered ring also deviates from planarity, while atom C1
Ê
is displaced from the S2/C2/C3/S3 mean plane by 0.122 (5) A.
Ê
The puckering parameters of this ring are Q = 0.077 (4) A and
' = 36 (3)ꢁ, so the dithiole ring assumes an envelope confor-
mation. The dihedral angle between the S2/C2/C3/S3 and C2/
C3/C4/C5 mean planes is 31.5 (2)ꢁ. No structure determina-
tions of molecules containing this heterocyclic system have
been reported previously. However, it has been stated that a
trace amount of the title compound was occasionally sepa-
rated as needle-shaped crystals and identi®ed by crystal
structure analysis (Lee & Noh, 1998).
coupling product, a fully unsaturated and tetra-phenyl-
È
È
substituted ET analogue, (II) (ErtasË & Ozturk, 2000), by
employing 1,8-diketone ring formation using P4S10 in the dark
È
È
(Ozturk, 1996), which proved that the 1,8-diketone ring
formation reaction is an ef®cient procedure for the synthesis
of fused and substituted 1,4-dithiine rings.
The bonds in the dithiole ring are very similar to those for
5-benzyl-5-phenyl[1,3]dithiolo[4,5-d][1,3]dithiole-2-thione
(Kaynak et al., 2001). The six-membered ring of the fused
heterocycle (dithiine, hereafter) is affected by the presence of
the phenyl substituents. The increase in the electron density of
the dithiine ring due to the phenyl groups has made the S5Ð
C4 and S4ÐC5 bond distances in (VII) [1.776 (4) and
Diketone (V) was prepared from the reaction of the readily
available dithiolate (III) (Svenstrup & Becher, 1995), with
desyl chloride in ethanol under a nitrogen atmosphere.
Surprisingly, when diketone (V) was re¯uxed in toluene, the
benzylphenyldithiole ring (VI) was obtained rather than the
desired dithiine ring (VII). The crystal structure of (VI) was
ꢀ
926 # 2001 International Union of Crystallography
Printed in Great Britain ± all rights reserved
Acta Cryst. (2001). C57, 926±928

organic compounds
Ê
1.802 (4) A, respectively] longer than the values of S5ÐC3
Ê
and S4ÐC2 [1.750 (5) and 1.741 (5) A, respectively]. In the
molecule, the double-bond distances are S1 C1 1.639 (5),
atmosphere was re¯uxed until the starting material had been
consumed, which took approximately 3 h. The solvent was then
evaporated under reduced pressure and the remaining viscous
material was chromatographed, eluting with hexane±dichloro-
Ê
C2 C3 1.341 (6) and C4 C5 1.337 (6) A. Similar bond
1
methane (3:1); m.p. 401±402 K (0.17 g, 25%). H NMR (200 MHz,
lengths have been reported for the crystal structures of 4,5-
(10,20-diphenylethylenedithio)-1,3-dithiole-2-thione (Lee
CDCl3): ꢁ 7.40±7.18 (8H, m, Ph), 6.92 (2H, d, J = 12 Hz, Ph), 3.76 (2H,
s, PhCH2); 13C NMR (50.32 Hz, CDCl3): ꢁ 205 (C S), 139, 134, 130,
128.8, 128.5, 127.8, 127.6, 127, 126, 86, 51; m/z (EI): 376 M+; found C
54.28, H 3.21%; C15H12S5 requires C 54.59, H 3.54%; UV: ꢂmax
(CH3CN, nm) 426.
&
Noh, 1998) and 5-benzyl-5-phenyl[1,3]dithiolo[4,5-d][1,3]-
dithiole-2-thione (Kaynak et al., 2001). The phenyl rings are
essentially planar [maximum deviations of 0.013 (6) and
Ê
0.006 (5) A for C9 and C16, respectively] and twisted out of
Preparation of 5,6-diphenyl[1,3]dithiolo[4,5-b][1,4]dithiine-2-
thione, (VII). The same reaction as for (VI) was repeated in the dark.
The crude material was puri®ed by column chromatography (3:1,
hexane/CH2Cl2), which gave 65% of (VII); m.p. 386±387 K. 1H NMR
(250 MHz, CDCl3): ꢁ 7.09±7.34 (m, 10 H); 13C NMR (67.8 MHz,
CDCl3): ꢁ 213.9 (C S), 136.2 (C-q), 134.7 (C-q), 129.9 (C-q), 129.5
(C-t), 128.7 (C-t), 128.6 (C-t); HRMS: m/z calculated 373.9386;
measured 373.9397 for C17H10S5; found C 54.44, H 2.66%: calculated
C 54.5, H 2.69%; IR: ꢃ 1080 cm 1 (C S); UV: ꢂmax (CH3CN, nm) 391.
the C2/C3/C4/C5 mean plane of the dithiine ring with torsion
angles of 53.6 (5) and 139.7 (4)ꢁ for S5ÐC4ÐC12ÐC17 and
S4ÐC5ÐC6ÐC7, respectively; the dihedral angle between
phenyl groups is 59.1 (2)ꢁ.
Crystal data
3
C17H10S5
Mr = 374.55
Monoclinic, P21/n
Dx = 1.499 Mg m
Cu Kꢅ radiation
Cell parameters from 19
re¯ections
Ê
a = 12.343 (2) A
ꢀ = 15.5±42.6ꢁ
ꢆ = 6.36 mm
T = 295 K
Ê
b = 5.273 (1) A
Ê
c = 26.029 (7) A
1
ꢄ = 101.54 (2)ꢁ
V = 1659.8 (6) A
Z = 4
3
Ê
Prismatic, light brown
0.48 Â 0.20 Â 0.12 mm
Data collection
Enraf±Nonius CAD-4 diffrac-
tometer
Rint = 0.075
ꢀmax = 74.2ꢁ
!/2ꢀ scans
h = 0 ! 15
Absorption correction: empirical
via scans (Fair, 1990)
Tmin = 0.272, Tmax = 0.466
3865 measured re¯ections
3393 independent re¯ections
2125 re¯ections with I > 2ꢇ(I)
k = 0 ! 6
l = 32 ! 31
3 standard re¯ections
frequency: 120 min
intensity decay: 1%
Figure 1
ORTEPIII (Johnson & Burnett, 2000) drawing of the asymmetric unit of
the title compound with the atomic numbering scheme. Displacement
ellipsoids are drawn at the 50% probability level.
Re®nement
Re®nement on F2
R‰F2 > 2ꢇꢂF2†Š = 0.058
wRꢂF2† = 0.149
w = 1/[ꢇ2(Fo2) + (0.0945P)2
+ 0.0036P],
In the title molecule, the shortest intermolecular contact is
Ê
where P = (Fo2 + 2Fc2)/3
(Á/ꢇ)max < 0.001
S2Á Á ÁS2(1 x, y, z) 3.305 (2) A, which is shorter than the
S = 1.06
sum of the van der Waals radii. Of particular note is the short
non-bonding intramolecular distances observed for H11Á Á ÁS4
3
Ê
2125 re¯ections
209 parameters
H-atom parameters constrained
Áꢈmax = 0.44 e A
3
Ê
0.44 e A
Áꢈmin
=
Ê
and H7Á Á ÁC12 of 2.77 and 2.74 A, respectively.
Experimental
Table 1
Selected geometric parameters (A, ).
ꢁ
Ê
Preparation of 2-[5-(2-oxo-1,2-diphenylethylsulfanyl)-2-thioxo-1,3-
dithiol-4-ylsulfanyl]-1,2-diphenyl-1-ethanone, (V). To a solution of
dithiolate (III) (0.26 g, 1 mmol) in dry ethanol (10 ml) and under a
nitrogen atmosphere was added desyl chloride, (IV) (0.5 g, 2 mmol),
dropwise and the solution was then stirred at room temperature for
3 h. The yellow precipitate was ®ltered and washed with ethanol
(5 ml), and was suf®ciently pure for use in the next step; m.p. 430±
431 K (0.57 g, 90%). 1H NMR (200 MHz, CDCl3): ꢁ 7.8 (20H, m, Ph),
6.1 (H, s, PhCHS), 5.8 (H, s, PhCHS); m/z (EI): 587 M+; found C
63.65, H 3.44%; C31H22O2S5 requires C 63.48, H 3.44%.
C1ÐS1
C1ÐS2
C1ÐS3
C2ÐC3
C2ÐS2
C2ÐS4
1.639 (5)
1.732 (5)
1.742 (5)
1.341 (6)
1.739 (4)
1.741 (5)
C3ÐS3
C3ÐS5
C4ÐC5
C4ÐS5
C5ÐS4
1.731 (5)
1.750 (5)
1.337 (6)
1.776 (4)
1.802 (4)
S1ÐC1ÐS2
S2ÐC1ÐS3
C3ÐC2ÐS2
C3ÐC2ÐS4
C2ÐC3ÐS3
C2ÐC3ÐS5
C5ÐC4ÐC12
123.9 (3)
112.6 (3)
116.0 (4)
122.3 (3)
117.1 (3)
121.2 (4)
125.6 (4)
C5ÐC4ÐS5
C4ÐC5ÐC6
C6ÐC7ÐC8
C1ÐS2ÐC2
C3ÐS3ÐC1
C2ÐS4ÐC5
C3ÐS5ÐC4
122.4 (3)
127.1 (4)
121.0 (5)
97.1 (2)
96.7 (2)
99.6 (2)
100.39 (19)
Preparation of 5-benzyl-5-phenyl[1,3]dithiolo[4,5-d][1,3]dithiole-
2-thione, (VI). A solution of 1,8-diketone (V) (1 g, 1.7 mmol) and
P4S10 (0.8 g, 1.70 mmol) in dry toluene (30 ml) under a nitrogen
ꢀ
Acta Cryst. (2001). C57, 926±928
F. Betul Kaynak et al. C17H10S5 927
È

organic compounds
Ê
Enraf±Nonius (1993). CAD-4 EXPRESS. Version 1.1. Nonius BV, Delft, The
Netherlands.
H atoms were placed geometrically 0.93 A from their parent atoms
and their displacement parameters were re®ned.
È
È
ErtasË, E. & Ozturk, T. (2000). Chem. Commun. pp. 2039±2040.
Fair, C. K. (1990). MolEN. Enraf±Nonius, Delft, The Netherlands.
Inoue, K., Tasaka, Y., Yamazaki, O., Nogami, T. & Mikama, H. (1986). Chem.
Lett. pp. 781±784.
Data collection: CAD-4 EXPRESS (Enraf±Nonius, 1993); data
reduction: MolEN (Fair, 1990); program(s) used to solve structure:
SIR (Burla et al., 1989) in MolEN; program(s) used to re®ne struc-
ture: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII
(Johnson & Burnett, 2000); software used to prepare material for
publication: PLATON (Spek, 1990).
Johnson, C. K. & Burnett, M. N. (2000). ORTEPIII. Report ORNL-6895. Oak
Ridge National Laboratory, Tennessee, USA.
È
Kaynak, F. B., Ozbey, S., Ozturk, T. & ErtasË, E. (2001). Acta Cryst. C57, 319±
È
È
320.
Lee, H.-J., Kim, Y.-Y. & Noh, D.-Y. (1998). Bull. Korean Chem. Soc. 19, 1011±
1013.
Lee, H.-J. & Noh, D.-Y. (1998). Bull. Korean Chem. Soc. 19, 340±344.
Noh, D.-Y., Lee, H.-J., Hong, J. & Underhill, A. E. (1996). Tetrahedron Lett. 37,
7603±7606.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FR1325). Services for accessing these data are
described at the back of the journal.
È
È
Ozturk, T. (1996). Tetrahedron Lett. 37, 2821±2824.
Sheldrick, G. M. (1997). SHELXL97. University of GoÈttingen, Germany.
Skabara, P. J., Serebryakov, I. M., Roberts, D. M., Perepichka, I. F., Coles, S. J.
& Hursthouse, M. B. (1999). J. Org. Chem. 64, 6418±6424.
Spek, A. L. (1990). Acta Cryst. A46, C-34.
Svenstrup, N. & Becher, J. (1995). Synthesis, pp. 215±235.
Williams, J. M., Beno, M. A., Wang, H. H, Leung, P. C. W., Emge, T. J., Geiser,
U. & Carlson, K. D. (1985). Acc. Chem. Res. 18, 261±267.
Yamada, J.-I., Satoki, S., Anzai, H., Hagiya, K., Tamura, M., Nishio, Y., Kajita,
K., Watanabe, E., Konno, M., Sato, T., Nishikawa, H. & Kikuchi, K. (1996).
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928 F. Betul Kaynak et al.
C17H10S5
Acta Cryst. (2001). C57, 926±928
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