A second polymorph of 3H-1,2-benzodi­thiole-3-thione

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

doi:10.1107/S2414314616017995

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161799

https://doi.org/10.1107/S2414314616017995

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A second polymorph of 3H-1,2-benzodithiole-3-thione

Khaled Boukebbous,^a ^* El Adoui Laifa,^a Aimery De Mallmann ^b and Mostafa Taoufik ^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 K. Fejfarova, Institute of Biotechnology CAS, Czech Republic (Received 26 October 2016; accepted 8 November 2016; online 18 November 2016)

The title compound, C₇H₄S₃, is crystallizes in the monoclinic space group P2₁/n; it is the second polymorph, the first having been reported recently in space group 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 space group C2/c (Boukebbous et al., 2016) whereas recrystallization in diethyl ether solution leads to a second polymorph in the monoclinic system, and space group 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°.

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.

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.

Figure 2
A view of the packing of the title compound, with displacement ellipsoids drawn at the 50% probability level. The inversion centre at [0,0,0] with symmetry operation (−x, −y, −z) is shown as orange dots. The twofold screw axis in the [010] direction at ( $[{1\over 4}]$ , y, $[{1\over 4}]$ ), with symmetry operation ( $[{1\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z), is shown as purple lines. The glide plane perpendicular to [010] with glide component [ $[{1\over 2}]$ , 0, $[{1\over 2}]$ ] and symmetry operation ( $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z) is shown as light-blue planes.

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

Figure 4
A view along the a axis of the molecular packing. S⋯S contacts are shown as dashed blue lines. H atoms have been omitted for clarity.

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 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 in the range 0.93–0.98 and N—H in the range 0.86–0.89 Å) and U_iso(H) (in the range 1.2–1.5 times U_eq of the parent atom), after which the positions were refined with riding constraints. (Cooper et al., 2010 ).

Table 1
Experimental details

Crystal data
Chemical formula	C₇H₄S₃
M_r	184.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	4.0062 (9), 10.739 (2), 17.178 (3)
β (°)	95.237 (18)
V (Å³)	736.0 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.91
Crystal size (mm)	0.52 × 0.10 × 0.06

Data collection
Diffractometer	Rigaku OD Xcalibur Atlas Gemini ultra
Absorption correction	Analytical [CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England.]$ ), based on expressions derived by Clark & Reid (1995 )]
T_min, T_max	0.724, 0.947
No. of measured, independent and observed [I > 2.0σ(I)] reflections	6569, 1832, 1482
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.694

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.101, 1.02
No. of reflections	1826
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.77, −0.65
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: 1515751

Crystal structure: contains datablocks global, New_Global_Publ_Block, I. DOI: https://doi.org/10.1107/S2414314616017995/ff4011sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616017995/ff4011Isup2.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) = 376
M_r = 184.31	D_x = 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

Data collection top

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	R_int = 0.053
Detector resolution: 10.4685 pixels mm^-1	θ_max = 29.6°, θ_min = 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
T_min = 0.724, T_max = 0.947	l = −23→23
6569 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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.101	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1]T_n-1(x)] where A_i are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] [1-(deltaF/6*sigmaF)²]² A_i are: 950. 0.135E + 04 758. 229.
S = 1.02	(Δ/σ)_max = 0.0002003
1826 reflections	Δρ_max = 0.77 e Å⁻³
91 parameters	Δρ_min = −0.65 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 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

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