organic compounds
A second polymorph of 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 title compound, C7H4S3, is crystallizes in the monoclinic P21/n; it is the second polymorph, the first having been reported recently in C2/c [Boukebbous et al. (2016) IUCrData, 1, x161688]. The molecule displays an almost planar geometry with two fused rings [S10—C3—C4—C9 torsion angle = 0.2 (5)°]. In the crystal, short S⋯S [3.555 (1) and 3.503 (1) Å] contacts and π–π aromatic stacking [shortest centroid–centroid separation = 4.006 (5) Å] sustain the three-dimensional molecular packing.
Keywords: crystal structure; polymorphs; 1,2-dithiole-3-thione derivatives; sulfur organic compounds; heterocyclic compounds.
CCDC reference: 1515751
Structure description
The title compound is a derivative of the 1,2-dithiole-3-thione family, which has attracted much interest because of the important bioactive properties and potential applications (Li et al., 2016, Russell et al., 2015), (Wallace et al., 2007). Recrystallization of 3H-1,2-benzodithiole-3-thione in toluene solution leads to a monoclinic polymorph in the C2/c (Boukebbous et al., 2016) whereas recrystallization in diethyl ether solution leads to a second polymorph in the monoclinic system, and P21/n (the present work). The 3H-1,2-benzodithiole-3-thione molecule is composed of an aromatic ring fused with five-membered ring that containing two S atoms and thione functional groups (Fig. 1). The molecule displays an almost planar geometry with two fused rings [S10—C3—C4—C9 = 0.2 (5)°] with bond lengths of 2.064 (1), 1.738 (4), 1.726 (4) and 1.645 (3) Å for S1—S2, C5—S1, C3—S2 and C3—S10 bonds, respectively, and values of 94.0 (1) and 98.3 (1)° observed for angles C5—S1—S2 and S1—S2—C3, respectively. The angle S2—C3—C4 [113.1 (2)°] deviates from the expected value of 120° for a Csp2 atom (C3=S10 bond). Likewise, a minor deviation (about 3°) is observed for the angles S1—C5—C4 and C5—C4—C3 from the expected value of 120°.
In the crystal (Figs. 2, 3 and 4), short S⋯S [S10⋯S1 = 3.555 (1) and S10⋯S2 = 3.503 (1) Å] contacts are observed. Moreover, parallel displaced π–π aromatic stacking interactions [shortest centroid-to-centroid separation = 4.006 (5) Å] linking adjacent molecules into a three-dimensional network are observed.
Synthesis and crystallization
The synthesis of 4.5-benzo-3H-1.2-dithiole-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), phosphorus pentasulfide (10 g, 0.04 mol) dissolved in xylene was added. The mixture was stirred for 1 h at reflux. The orange precipitate that formed was washed successively with distilled water and cold ethanol at 273 K and dried at room temperature for several hours. The recrystallization process was performed from diethyl ether solution by slow evaporation and red needles 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 in the range 0.93–0.98 and N—H in the range 0.86–0.89 Å) and Uiso(H) (in the range 1.2–1.5 times Ueq of the parent atom), after which the positions were refined with riding constraints. (Cooper et al., 2010).
details are summarized in Table 1Structural data
CCDC reference: 1515751
https://doi.org/10.1107/S2414314616017995/ff4011sup1.cif
contains datablocks global, New_Global_Publ_Block, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616017995/ff4011Isup2.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) = 376 |
Mr = 184.31 | Dx = 1.663 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1997 reflections |
a = 4.0062 (9) Å | θ = 4.0–28.7° |
b = 10.739 (2) Å | µ = 0.91 mm−1 |
c = 17.178 (3) Å | T = 150 K |
β = 95.237 (18)° | Needle, red |
V = 736.0 (3) Å3 | 0.52 × 0.10 × 0.06 mm |
Z = 4 |
Rigaku OD Xcalibur Atlas Gemini ultra diffractometer | 1832 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 1482 reflections with I > 2.0σ(I) |
Graphite monochromator | Rint = 0.053 |
Detector resolution: 10.4685 pixels mm-1 | θmax = 29.6°, θmin = 3.1° |
ω scans | h = −5→5 |
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)] | k = −14→14 |
Tmin = 0.724, Tmax = 0.947 | l = −23→23 |
6569 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)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.101 | Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 950. 0.135E + 04 758. 229. |
S = 1.02 | (Δ/σ)max = 0.0002003 |
1826 reflections | Δρmax = 0.77 e Å−3 |
91 parameters | Δρmin = −0.65 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 0.1K. Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.3003 (2) | 0.52792 (8) | 0.39805 (5) | 0.0270 | |
S2 | 0.2657 (2) | 0.54353 (8) | 0.27784 (5) | 0.0258 | |
C3 | 0.0569 (8) | 0.6841 (3) | 0.26919 (19) | 0.0228 | |
C4 | −0.0083 (8) | 0.7372 (3) | 0.34414 (18) | 0.0199 | |
C5 | 0.1038 (8) | 0.6697 (3) | 0.41121 (18) | 0.0211 | |
C6 | 0.0514 (9) | 0.7144 (4) | 0.48597 (19) | 0.0271 | |
C7 | −0.1163 (9) | 0.8257 (4) | 0.4917 (2) | 0.0303 | |
C8 | −0.2306 (9) | 0.8936 (4) | 0.4254 (2) | 0.0302 | |
C9 | −0.1787 (8) | 0.8500 (3) | 0.3520 (2) | 0.0238 | |
S10 | −0.0445 (3) | 0.73941 (10) | 0.18088 (5) | 0.0327 | |
H61 | 0.1275 | 0.6685 | 0.5306 | 0.0328* | |
H71 | −0.1565 | 0.8563 | 0.5416 | 0.0356* | |
H81 | −0.3459 | 0.9684 | 0.4305 | 0.0358* | |
H91 | −0.2554 | 0.8942 | 0.3071 | 0.0286* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0281 (4) | 0.0246 (4) | 0.0274 (4) | 0.0007 (3) | −0.0027 (3) | 0.0049 (3) |
S2 | 0.0258 (4) | 0.0255 (4) | 0.0256 (4) | −0.0001 (3) | 0.0007 (3) | −0.0043 (3) |
C3 | 0.0195 (14) | 0.0253 (16) | 0.0231 (15) | −0.0043 (13) | −0.0010 (12) | 0.0012 (13) |
C4 | 0.0195 (14) | 0.0208 (15) | 0.0195 (14) | −0.0047 (12) | 0.0014 (11) | 0.0001 (12) |
C5 | 0.0202 (14) | 0.0249 (16) | 0.0178 (14) | −0.0044 (13) | −0.0003 (12) | 0.0021 (12) |
C6 | 0.0288 (17) | 0.0327 (18) | 0.0197 (15) | −0.0087 (15) | 0.0012 (13) | 0.0022 (14) |
C7 | 0.0315 (18) | 0.037 (2) | 0.0236 (16) | −0.0089 (16) | 0.0090 (14) | −0.0076 (15) |
C8 | 0.0275 (17) | 0.0282 (18) | 0.0357 (19) | −0.0018 (15) | 0.0076 (15) | −0.0047 (15) |
C9 | 0.0204 (15) | 0.0251 (17) | 0.0260 (16) | −0.0030 (13) | 0.0029 (13) | 0.0058 (13) |
S10 | 0.0417 (5) | 0.0381 (5) | 0.0175 (4) | −0.0030 (4) | −0.0016 (3) | 0.0039 (4) |
S1—S2 | 2.0637 (13) | C6—C7 | 1.379 (5) |
S1—C5 | 1.738 (4) | C6—H61 | 0.938 |
S2—C3 | 1.726 (4) | C7—C8 | 1.394 (5) |
C3—C4 | 1.453 (4) | C7—H71 | 0.945 |
C3—S10 | 1.645 (3) | C8—C9 | 1.378 (5) |
C4—C5 | 1.400 (4) | C8—H81 | 0.935 |
C4—C9 | 1.403 (5) | C9—H91 | 0.935 |
C5—C6 | 1.404 (5) | ||
S2—S1—C5 | 93.97 (11) | C5—C6—H61 | 120.2 |
S1—S2—C3 | 98.33 (12) | C7—C6—H61 | 121.4 |
S2—C3—C4 | 113.1 (2) | C6—C7—C8 | 121.4 (3) |
S2—C3—S10 | 118.2 (2) | C6—C7—H71 | 119.5 |
C4—C3—S10 | 128.7 (3) | C8—C7—H71 | 119.2 |
C3—C4—C5 | 117.1 (3) | C7—C8—C9 | 120.2 (3) |
C3—C4—C9 | 123.6 (3) | C7—C8—H81 | 120.1 |
C5—C4—C9 | 119.3 (3) | C9—C8—H81 | 119.7 |
C4—C5—S1 | 117.5 (2) | C4—C9—C8 | 119.8 (3) |
C4—C5—C6 | 120.8 (3) | C4—C9—H91 | 119.0 |
S1—C5—C6 | 121.7 (3) | C8—C9—H91 | 121.2 |
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
Boukebbous, K., Laifa, E. A. & De Mallmann, A. (2016). IUCrData, 1, x161688. Google Scholar
Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897. CrossRef CAS Web of Science IUCr Journals Google Scholar
Cooper, R. I., Thompson, A. L. & Watkin, D. J. (2010). J. Appl. Cryst. 43, 1100–1107. Web of Science CrossRef CAS IUCr Journals Google Scholar
Klingsberg, E. & Schreiber, A. M. (1962). J. Am. Chem. Soc. 84, 2941–2944. CrossRef CAS Web of Science 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. Web of Science CrossRef CAS Google Scholar
Wallace, J. L., Caliendo, G., Santagada, V., Cirino, G. & Fiorucci, S. (2007). Gastroenterology, 132, 261–271. CrossRef CAS Google Scholar
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, UK. 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.