5-benzyl-5-phenyl[1,3]dithiolo[4,5-d]-[1,3]dithiole-2-thione

Article abstract of DOI:10.1107/S0108270100019764

In the title compound, C₁₇H₁₂S₅, the dithiole ring bearing the aryl substituents assumes an envelope conformation with the maximum deviation from planarity being -0.053 A. The phenyl and benzyl rings are twisted by 33.0 (1

Full text of DOI:10.1107/S0108270100019764

organic compounds
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Acta Crystallographica Section C
Crystal Structure
are Q = 0.469 (3) A and ' = 321.8 (4) , so the dithiole ring
assumes an envelope conformation. The mean bond distances
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in the dithiole±thione ring are S C = 1.640 (4) A and SÐ
Communications
2
Csp = 1.732 (4) A. These values are comparable with those
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ISSN 0108-2701
found in the structures of both 6-(4-methoxyphenyl)-
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thieno[2,3-d][1,3]dithiole-2-thione (Ozturk & Wallis, 1996)
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5-Benzyl-5-phenyl[1,3]dithiolo[4,5-d]-
[1,3]dithiole-2-thione
a
a
b
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F. Betul Kaynak, Suheyla Ozbey, * Turan Ozturk and
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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 16 October 2000
Accepted 5 December 2000
In the title compound, C17H12S5, the dithiole ring bearing the
aryl substituents assumes an envelope conformation with the
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maximum deviation from planarity being 0.053 A. The
phenyl and benzyl rings are twisted by 33.0 (1) and 31.1 (1)ꢀ,
respectively, out of the dithiole plane. The crystal packing is
governed by short SÁ Á ÁS interactions, with the shortest being
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3.550 (2) A.
Comment
During the course of our studies on synthesizing new bis-
(ethylenedithio)tetrathiafulvalene [BEDT±TTF or ET, (I)]
derivatives, radical cation salts which show electrical conduc-
tivity and in some cases superconductivity (Williams et al.,
1985), we have focused on the recently developed reactions of
and 5,6-diphenylthieno[2,3-d][1,3]dithiole-2-thione (Kaynak
et al., 2000). The other dithiole ring of the fused heterocycle is
affected by the presence of the phenyl and benzyl substituents.
The bond lengths are quite different from those of the adja-
cent dithiole ring; the mean SÐCsp2 and SÐCsp3 bond
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Lawesson's reagent (LR), (II) (Ozturk, 1996; Ozturk & Wallis,
1996), or phosphorus pentasul®de, P4S10, with 1,8-diketones
(III). These reactions have proved to be an ef®cient route to
the synthesis of substituted thiophene (IV) and 1,4-dithiin (V)
heterocyclic systems, which could be useful building blocks for
new BEDT±TTF derivatives.
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lengths are 1.748 (1) and 1.855 (14) A, respectively. The
shortening of the S5ÐC4 and C4ÐC5 distances versus S4ÐC4
and C4ÐC11 may be explained by the two short intramole-
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In an attempt to synthesize the 5,6-diphenyl derivative (VI)
of BEDT±TTF, tetraphenyl-1,8-diketone (VIII), which was
prepared from the reaction of readily available dithiolate
(VII) (Svenstrup & Becher, 1995) with desyl chloride, was
treated with both LR and P4S10. In accordance with the result
obtained by Lee et al. (1998), diphenylthiophene (IX) rather
than diphenyldithiin (VI) was isolated when the reaction was
performed with LR. Surprisingly, when the reaction was
carried out with P4S10 under the same conditions, benzyl-
phenyldithiole (X) ring formed along with (IX).
cular contacts H10Á Á ÁS5 (2.58 A) and H112Á Á ÁC6 (2.63 A).
In the title compound, (X), with the exception of the C4
atom, the fused heterocycle is nearly planar, with a dihedral
angle between the S5/C3/C2/S4 and C1/S2/C2/C3/S3 mean
planes of 3.02 (8)ꢀ. The thiole ring which bears the aryl
substituents deviates from planarity, while atom C4 is
Figure 1
ORTEP (Johnson, 1965) drawing with the atomic numbering scheme. The
displacement ellipsoids are drawn at the 30% probability level.
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displaced from the S5/C3/C2/S4 mean plane by 0.736 (4) A.
The puckering parameters (Cremer & Pople, 1975) of this ring
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Acta Cryst. (2001). C57, 319±320
# 2001 International Union of Crystallography
Printed in Great Britain ± all rights reserved 319

organic compounds
Re®nement
The substituted phenyl rings are essentially planar
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[maximum deviations of 0.002 (4) and 0.010 (4) A for C8
Re®nement on F
R = 0.047
wR = 0.054
w = 1/[ꢅ2(F) + (0.02F)2 + 0.85],
except w = 0 if F2 < cutoff Â
ꢅ2F, cutoff = 3.0
and C14, respectively] and twisted slightly out of the plane of
the fused heterocycle, with torsion angles of 175.4 (3) and
170.5 (3)ꢀ for S5ÐC4ÐC5ÐC6 and S4ÐC4ÐC11ÐC12,
respectively. The dihedral angles between the phenyl groups
(C5±C10 and C12±C17) and the S5/C3/C2/S4 mean plane are
33.0 (1) and 31.1 (1)ꢀ, respectively, while the dihedral angle
between these two phenyl groups is 61.5 (1)ꢀ.
S = 0.95
(Á/ꢅ)max < 0.001
3
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2513 re¯ections
199 parameters
H-atom parameters constrained
Áꢆmax = 0.41 e A
3
Ê
0.45 e A
Áꢆmin
=
Table 1
Selected geometric parameters (A, ).
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In the crystal, the molecules are packed in layers related by
the translation [001]. The relevant SÁ Á ÁS non-bonding contacts
S1ÐC1
S2ÐC1
S2ÐC2
S3ÐC1
S3ÐC3
S4ÐC2
S4ÐC4
1.640 (4)
1.729 (4)
1.733 (4)
1.736 (4)
1.731 (4)
1.747 (4)
1.865 (4)
S5ÐC3
S5ÐC4
C2ÐC3
C4ÐC5
C4ÐC11
C11ÐC12
1.748 (4)
1.845 (3)
1.336 (5)
1.513 (5)
1.533 (4)
1.500 (5)
1
2
1
2
involved are S1Á Á ÁS2(2 x,
y,
z) = 3.772 (2),
S2Á Á ÁS3(x, 1 + y, z) = 3.601 (2), S3Á Á ÁS4(x, 1 + y, z) =
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3.630 (2) and S4Á Á ÁS5(x, 1 + y, z) = 3.550 (2) A.
Experimental
C1ÐS2ÐC2
C1ÐS3ÐC3
C2ÐS4ÐC4
C3ÐS5ÐC4
S1ÐC1ÐS2
S1ÐC1ÐS3
S2ÐC1ÐS3
S2ÐC2ÐS4
S2ÐC2ÐC3
96.3 (2)
96.6 (2)
92.8 (2)
S4ÐC2ÐC3
S3ÐC3ÐS5
S3ÐC3ÐC2
S5ÐC3ÐC2
S4ÐC4ÐS5
S4ÐC4ÐC5
S4ÐC4ÐC11
S5ÐC4ÐC11
C4ÐC11ÐC12
116.9 (3)
125.7 (2)
116.3 (3)
117.9 (3)
105.0 (2)
106.9 (2)
108.7 (2)
109.5 (2)
115.0 (3)
Preparation of 2-[5-(2-oxo-1,2-diphenylethylsulfanyl)-2-thioxo-1,3-
dithiol-4-ylsulfanyl]-1,2-diphenyl-1-ethanone, (VIII). To a solution of
dithiolate (VII) (0.26 g, 1 mmol) in dry ethanol (10 ml) and under a
nitrogen atmosphere, desyl chloride (0.5 g, 2 mmol) was added
dropwise. The solution was then stirred at room temperature for 3 h.
The yellow precipitate was ®ltered off and washed with ethanol
(5 ml), which 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%.
92.3 (2)
123.0 (2)
123.5 (3)
113.4 (2)
126.0 (2)
117.2 (3)
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Ring-H atoms were placed geometrically 0.95 A from their parent
atoms, while the positions of atoms H111 and H112 were taken from a
difference map. A riding model was used for all ring-H atoms, with
Ueq(H) = 1.3Ueq(C). The same model was also applied for the H
atoms on C11 and after re®ning for a few cycles isotropically, they
were ®xed.
Preparation of 5-benzyl-5-phenyl[1,3]dithiolo[4,5-d][1,3]dithiole-
2-thione, (X). A solution of 1,8-diketone (VIII) (1 g, 1.7 mmol) and
P4S10 (0.8 g, 1.70 mmol) in dry toluene (30 ml) under a nitrogen
atmosphere was re¯uxed until consumption of the starting material
was complete, which took approximately 5 h. The solvent was then
evaporated under reduced pressure and the remaining viscous
material was chromatographed, eluting with hexane±dichloro-
methane (3:1). The ®rst fraction yielded 5,6-diphenylthieno[2,3-
d][1,3]dithiole-2-thione, (IX) (0.23 g, 40%), and the second fraction
Data collection: CAD-4 Software (Enraf±Nonius, 1993); data
reduction: MolEN (Fair, 1990); program(s) used to solve structure:
SIR in MolEN; program(s) used to re®ne structure: LSFM (Fair,
1990); molecular graphics: ORTEP (Johnson, 1965); software used to
prepare material for publication: MolEN.
1
was characterized as (X), m.p. 401±402 K (0.17 g, 25%). H NMR
(200 MHz, 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: (CH3CN, nm) 426.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FR1309). Services for accessing these data are
described at the back of the journal.
Crystal data
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C17H12S5
Mr = 376.62
Monoclinic, P21/c
Dx = 1.48 Mg m
Cu Kꢂ radiation
Cell parameters from 25
re¯ections
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References
a = 14.178 (3) A
b = 6.3433 (6) A
ꢃ = 22.2±42.7ꢀ
ꢄ = 6.23 mm
T = 295 K
Ê
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354±1358.
Enraf±Nonius (1993). CAD-4 Software. Version 1.1. Enraf±Nonius, Delft, The
Netherlands.
1
Ê
c = 19.227 (3) A
ꢁ = 101.538 (15)ꢀ
3
Ê
V = 1694.2 (5) A
Z = 4
Prismatic, brown
0.30 Â 0.15 Â 0.09 mm
Fair, C. K. (1990). MolEN. Enraf±Nonius, Delft, The Netherlands.
Johnson, C. K. (1965). ORTEP. Report ORNL-3794. Oak Ridge National
Laboratory, Tennessee, USA.
Data collection
È
È
È
Kaynak, F. B., Ozbey, S., Ozturk, T. & ErtasË, E. (2000). Unpublished results.
Lee, H.-J., Kim, Y.-Y. & Noh, D.-Y. (1998). Bull. Korean Chem. Soc. 19, 1011±
1013.
Enraf±Nonius CAD-4 diffract-
ometer
Rint = 0.048
max = 74.4ꢀ
ꢃ
!/2ꢃ scans
h = 17 ! 17
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351±
359.
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È
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Ozturk, T. & Wallis, J. D. (1996). Acta Cryst. C52, 2552±2554.
Svenstrup, N. & Becher, J. (1995). Synthesis, p. 215.
Absorption correction: empirical
via scans (North et al., 1968)
Tmin = 0.171, Tmax = 0.571
3891 measured re¯ections
3448 independent re¯ections
2513 re¯ections with I > 3ꢅ(I)
k = 0 ! 7
l = 23 ! 0
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Ozturk, T. (1996). Tetrahedron Lett. 37, 2821±2824.
3 standard re¯ections
frequency: 120 min
intensity decay: 1%
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.
ꢁ
320 F. Betul Kaynak et al.
C17H12S5
Acta Cryst. (2001). C57, 319±320
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