3H-1,2-Benzodi­thiole-3-thione

Boukebbous, K.; Laifa, E.A.; De Mallmann, A.

doi:10.1107/S2414314616016886

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 10| October 2016| x161688

https://doi.org/10.1107/S2414314616016886

Open

access

3H-1,2-Benzodithiole-3-thione

Khaled Boukebbous,^a ^* El Adoui Laifa ^a and Aimery De Mallmann ^b

^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

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 20 October 2016; accepted 20 October 2016; online 25 October 2016)

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 functional group (Fig. 1). 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).

Figure 1
The title compound, with displacement ellipsoids drawn at the 50% probability level.

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 (Figs. 2 and 3).

Figure 2
The crystal packing of the title compound, with displacement ellipsoids drawn at the 50% probability level. Inversion centres at [0,0,0] and [1/4,1/4,0] with symmetry operations of (−x, −y, −z) and ( $[{1\over 2}]$ − x, $[{1\over 2}]$ − y, −z), respectively, are shown as orange dots. Rotation and screw axes in the [010] direction at (0, y, 1/4) and (1/4, y, 1/4) with symmetry operations of (−x, y, $[{1\over 2}]$ − z) and ( $[{1\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z), respectively, are shown as purple lines.

Figure 3
A view along the c axis of the packing. The shortest van der Waals interactions are shown as dashed blue lines.

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 refinement details are summarized in Table 1. 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 U_iso(H) values (in the range 1.2–1.5 times U_eq of the parent atom), after which the positions were refined with riding constraints.

Table 1
Experimental details

Crystal data
Chemical formula	C₇H₄S₃
M_r	184.28
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	13.1921 (9), 7.5999 (5), 15.2507 (11)
β (°)	105.223 (7)
V (Å³)	1475.36 (18)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.91
Crystal size (mm)	0.37 × 0.16 × 0.14

Data collection
Diffractometer	Oxford Diffraction Xcalibur Atlas Gemini ultra
Absorption correction	Multi-scan [empirical absorption correction using spherical harmonics (Clark & Reid, 1995 )]
T_min, T_max	0.602, 0.815
No. of measured, independent and observed [I > 2.0σ(I)] reflections	17502, 1969, 1784
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.174, 1.04
No. of reflections	1965
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.67
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England.]$ ), SIR97 (Altomare et al., 1999 ), CRYSTALS (Betteridge et al., 2003 ) and CAMERON (Watkin et al., 1996 ).

Structural data

CCDC reference: 1510917

Crystal structure: contains datablocks global, New_Global_Publ_Block, I. DOI: https://doi.org/10.1107/S2414314616016886/hb4088sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616016886/hb4088Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: 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).

(I) top

Crystal data top

C₇H₄S₃	F(000) = 752
M_r = 184.28	D_x = 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

Data collection top

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	R_int = 0.070
Detector resolution: 10.4685 pixels mm^-1	θ_max = 29.6°, θ_min = 3.1°
ω scans	h = −17→18
Absorption correction: multi-scan Empirical absorption correction using spherical harmonics, (Clark & Reid, 1995)	k = −10→10
T_min = 0.602, T_max = 0.815	l = −20→20
17502 measured reflections

Refinement top

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(F_o²,0) + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.0003912
1965 reflections	Δρ_max = 0.80 e Å⁻³
91 parameters	Δρ_min = −0.67 e Å⁻³
0 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487. Web of Science CrossRef IUCr Journals Google Scholar
Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897. CrossRef CAS Web of Science IUCr Journals Google Scholar
Klingsberg, E. & Schreiber, A. M. (1962). J. Am. Chem. Soc. 84, 2941–2944. CrossRef CAS Google Scholar
Li, K. R., Yang, S. Q., Gong, Y. Q., Yang, H., Li, X. M., Zhao, Y. X., Yao, J., Jiang, Q. & Cao, C. (2016). Sci. Rep. 6, 13. Google Scholar
Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England. Google Scholar
Russell, G. K., Gupta, R. C. & Vadhanam, M. V. (2015). Mutat. Res./Fundam. Mol. Mech. Mutagen. 774, 25–32. CrossRef CAS Google Scholar
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.