organic compounds
3H-1,2-Benzodithiole-3-thione
aDepartment of Chemistry, University of Constantine, BP, 325 Route de Ain El Bey, Constantine 25017, Algeria, and bC2P2 (CNRS-UMR 5265), COMS group, Lyon 1 University, ESCPE Lyon, 43 Boulevard du 11 Novembre 1918, Villeurbanne 69626, France
*Correspondence e-mail: boukebbous.khaled@gmail.com
The almost planar (r.m.s. deviation = 0.034 Å) title compound, C7H4S3, was synthesized by reacting 2,2-dithiodibenzoic acid with phosphorus pentasulfide in xylene solution. In the crystal, short S⋯S [3.3727 (14), 3.3765 (13) and 3.4284 (13) Å] contacts and aromatic π–π stacking [shortest centroid–centroid separation = 3.618 (2) Å] are observed.
Keywords: crystal structure; dithiolethione derivatives; sulfur organic compounds; heterocyclic compounds.
CCDC reference: 1510917
Structure description
The title compound belongs to the 1,2-dithiole-3-thione family, which has attracted recent interest because of the bioactive properties and potential applications of its members (Li et al., 2016; Russell et al., 2015).
The title compound is composed of a benzene ring fused with a five-membered ring containing two S atoms and a thione ). The geometry of the molecule is almost planar (r.m.s. deviation = 0.034 Å), with bond lengths of 2.064 (1), 1.751 (3), 1.732 (3) and 1.654 (4) Å for S1—S2, C5—S1, C3—S2 and C3—S10, respectively. Furthermore, bond angles of 93.62 (12) and 98.24 (12)° are observed for C5—S1—S2 and S1—S2—C3, respectively. The S2—C3—C4 angle [113.5 (2)°] deviates from the expected value of 120° for a Csp2 atom (C3=S10); similarly, minor deviations of −3° are observed for the angles S1—C5—C4 and C5—C4—C3 from the expected value of 120° (C4=C5).
(Fig. 1In the crystal, short S⋯S [3.3727 (14), 3.3765 (13) and 3.4284 (13) Å] contacts and aromatic π–π stacking [shortest centroid–centroid separation = 3.618 (2) Å] are observed (Figs. 2 and 3).
Synthesis and crystallization
The synthesis of 3H-1,2-benzodithiole-3-thione was based on a previously reported method (Klingsberg & Schreiber, 1962). To a xylene solution (150 ml) of 2,2-dithiodibenzoic acid (10 g, 0.033 mol) was added phosphorus pentasulfide (10 g, 0.04 mol) dissolved in xylene. The mixture was stirred for 1 h under reflux. The orange precipitate which formed was washed with distilled water and cold ethanol at 273 K successively and dried at room temperature for several hours. The recrystallization process was performed from toluene solution and red plates in a yield of 80% were obtained.
Refinement
Crystal data, data collection and structure . The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H = 0.93–0.98 Å and N—H = 0.86–0.89 Å) and Uiso(H) values (in the range 1.2–1.5 times Ueq of the parent atom), after which the positions were refined with riding constraints.
details are summarized in Table 1Structural data
CCDC reference: 1510917
https://doi.org/10.1107/S2414314616016886/hb4088sup1.cif
contains datablocks global, New_Global_Publ_Block, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616016886/hb4088Isup2.hkl
Data collection: CrysAlis PRO (Rigaku OD, 2015); cell
CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).C7H4S3 | F(000) = 752 |
Mr = 184.28 | Dx = 1.659 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 16526 reflections |
a = 13.1921 (9) Å | θ = 3.4–29.4° |
b = 7.5999 (5) Å | µ = 0.91 mm−1 |
c = 15.2507 (11) Å | T = 150 K |
β = 105.223 (7)° | Plate, red |
V = 1475.36 (18) Å3 | 0.37 × 0.16 × 0.14 mm |
Z = 8 |
Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer | 1969 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 1784 reflections with I > 2.0σ(I) |
Graphite monochromator | Rint = 0.070 |
Detector resolution: 10.4685 pixels mm-1 | θmax = 29.6°, θmin = 3.1° |
ω scans | h = −17→18 |
Absorption correction: multi-scan Empirical absorption correction using spherical harmonics, (Clark & Reid, 1995) | k = −10→10 |
Tmin = 0.602, Tmax = 0.815 | l = −20→20 |
17502 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.059 | H-atom parameters constrained |
wR(F2) = 0.174 | Method = Modified Sheldrick w = 1/[σ2(F2) + ( 0.09P)2 + 10.33P] , where P = (max(Fo2,0) + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.0003912 |
1965 reflections | Δρmax = 0.80 e Å−3 |
91 parameters | Δρmin = −0.67 e Å−3 |
0 restraints |
Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1 K. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.58588 (7) | 0.30591 (11) | 0.64939 (6) | 0.0267 | |
S2 | 0.71762 (6) | 0.15998 (11) | 0.71004 (6) | 0.0256 | |
C3 | 0.7343 (3) | 0.0566 (4) | 0.6136 (2) | 0.0236 | |
C4 | 0.6570 (3) | 0.1061 (4) | 0.5317 (2) | 0.0227 | |
C5 | 0.5785 (3) | 0.2235 (4) | 0.5407 (2) | 0.0234 | |
C6 | 0.4972 (3) | 0.2718 (5) | 0.4651 (2) | 0.0272 | |
C7 | 0.4986 (3) | 0.2065 (5) | 0.3811 (3) | 0.0310 | |
C8 | 0.5770 (3) | 0.0912 (5) | 0.3711 (2) | 0.0304 | |
C9 | 0.6559 (3) | 0.0407 (4) | 0.4456 (2) | 0.0248 | |
S10 | 0.83218 (7) | −0.08475 (12) | 0.62490 (6) | 0.0310 | |
H91 | 0.7081 | −0.0376 | 0.4393 | 0.0301* | |
H81 | 0.5773 | 0.0501 | 0.3136 | 0.0362* | |
H71 | 0.4450 | 0.2388 | 0.3300 | 0.0373* | |
H61 | 0.4433 | 0.3466 | 0.4714 | 0.0335* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0287 (4) | 0.0234 (4) | 0.0270 (4) | 0.0048 (3) | 0.0053 (3) | −0.0032 (3) |
S2 | 0.0261 (4) | 0.0260 (4) | 0.0238 (4) | 0.0021 (3) | 0.0049 (3) | −0.0008 (3) |
C3 | 0.0255 (15) | 0.0216 (14) | 0.0255 (15) | −0.0018 (12) | 0.0101 (12) | 0.0000 (11) |
C4 | 0.0284 (15) | 0.0155 (13) | 0.0247 (15) | −0.0022 (11) | 0.0075 (12) | 0.0000 (11) |
C5 | 0.0273 (15) | 0.0174 (14) | 0.0252 (15) | −0.0007 (11) | 0.0062 (12) | −0.0024 (11) |
C6 | 0.0274 (16) | 0.0236 (16) | 0.0290 (16) | 0.0032 (12) | 0.0046 (13) | 0.0017 (12) |
C7 | 0.0323 (18) | 0.0271 (17) | 0.0297 (17) | −0.0013 (14) | 0.0015 (13) | 0.0022 (13) |
C8 | 0.0389 (19) | 0.0250 (16) | 0.0273 (16) | −0.0036 (14) | 0.0088 (14) | −0.0023 (13) |
C9 | 0.0288 (16) | 0.0190 (14) | 0.0281 (15) | −0.0013 (12) | 0.0101 (12) | −0.0008 (12) |
S10 | 0.0310 (5) | 0.0303 (5) | 0.0329 (5) | 0.0098 (3) | 0.0105 (4) | 0.0044 (3) |
S1—S2 | 2.0644 (12) | C6—C7 | 1.379 (5) |
S1—C5 | 1.751 (3) | C6—H61 | 0.935 |
S2—C3 | 1.731 (3) | C7—C8 | 1.394 (5) |
C3—C4 | 1.440 (5) | C7—H71 | 0.937 |
C3—S10 | 1.653 (3) | C8—C9 | 1.379 (5) |
C4—C5 | 1.401 (5) | C8—H81 | 0.932 |
C4—C9 | 1.401 (5) | C9—H91 | 0.934 |
C5—C6 | 1.401 (5) | ||
S2—S1—C5 | 93.62 (12) | C5—C6—H61 | 120.9 |
S1—S2—C3 | 98.24 (12) | C7—C6—H61 | 120.6 |
S2—C3—C4 | 113.5 (2) | C6—C7—C8 | 121.3 (3) |
S2—C3—S10 | 118.5 (2) | C6—C7—H71 | 119.2 |
C4—C3—S10 | 128.0 (3) | C8—C7—H71 | 119.5 |
C3—C4—C5 | 117.1 (3) | C7—C8—C9 | 120.4 (3) |
C3—C4—C9 | 123.5 (3) | C7—C8—H81 | 120.1 |
C5—C4—C9 | 119.4 (3) | C9—C8—H81 | 119.5 |
S1—C5—C4 | 117.5 (2) | C4—C9—C8 | 119.6 (3) |
S1—C5—C6 | 121.7 (3) | C4—C9—H91 | 119.7 |
C4—C5—C6 | 120.8 (3) | C8—C9—H91 | 120.7 |
C5—C6—C7 | 118.4 (3) |
Acknowledgements
We are grateful to The French National Center for Scientific Research (CNRS) for financial support.
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