4,5-Di­chloro-3H-1,2-di­thiol-3-one

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

doi:10.1107/S2414314616018204

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161820

https://doi.org/10.1107/S2414314616018204

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4,5-Dichloro-3H-1,2-dithiol-3-one

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 S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 25 October 2016; accepted 13 November 2016; online 18 November 2016)

The crystallization from an ethyl acetate solution of the title compound, also known as dichloro-1,2-dithiacyclopentenone, C₃Cl₂OS₂, leads to a monoclinic system with P2₁/n space group. The molecule displays an almost planar geometry, with a torsion angle of −2.1 (1)° for the endocyclic C—C—S—S fragment. The S—S and C=O bond lengths are 2.0521 (8) and 1.212 (3) Å, respectively. The endocyclic S—C—C angle sustained by the carbonyl group, 110.94 (16)°, deviates from the expected value of 120° for an sp²-hybridized C atom. In the crystal, short S⋯S, S⋯Cl, S⋯O and Cl⋯Cl contacts are observed.

Keywords: crystal structure; 1,2-dithiol-3-one; sulfur organic compounds; heterocyclic compounds.

CCDC reference: 1517056

Structure description

The title compound belongs to a family of bioactive compounds (He et al., 2004 ). Its crystallization from an ethyl acetate solution leads to a monoclinic system with P2₁/n space group (Figs. 1 and 2). The molecule is almost planar, with torsion angles of −0.3 (3), 0.6 (3), −2.1 (1), −0.8 (2) and −0.6 (3)° for the Cl6—C5= C4—Cl7, Cl7—C4—C3=O8, C4—C3—S2—S1, C4=C5—S1—S2 and S1—C5=C4—C3 fragments, respectively. Bond lengths of 2.0521 (8), 1.728 (2), 1.785 (2), 1.696 (2), 1.707 (2), and 1.212 (3) Å, respectively, for the S1—S2, C5—S1, C3—S2, C5—Cl6, C4—Cl7 and C3=O8 bonds are observed; furthermore, values of 93.88 (8) and 97.60 (8)° for the C5—S1—S2 and S1—S2—C3 angles, respectively, are noted. The endocyclic angle at C3, 110.94 (16)°, deviates from the value of 120° expected for an sp²-hybridized carbon atom (C3=O8 bond); similarly, minor deviations (less than 2°) are observed for the angles S1—C5=C4 and C3—C4=C5 from the expected value of 120° for these sp² C atoms (C4=C5 bond).

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

Figure 2
Crystal packing view 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 parallel to [010] 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.

In the crystal, short S⋯S [3.5929 (11) Å], S⋯Cl [3.4162 and 3.5219 (11) Å], S⋯O [3.153 (2) and 3.140 (2) Å] and Cl⋯Cl [3.3390 (11) Å] contacts are observed (Fig. 3).

Figure 3
A view along the b axis showing the molecular packing. Displacement ellipsoids are drawn at the 50% probability level. Short interactions are shown as dashed blue lines.

Synthesis and crystallization

A commercial sample (Matrix Scientific) of 4,5-dichloro-3H-1,2-dithiol-3-one was used. The crystallization was performed using an ethyl acetate solution with a slow evaporation process, affording suitable single crystals.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₃Cl₂OS₂
M_r	187.07
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	8.678 (2), 7.9332 (14), 8.7340 (18)
β (°)	98.62 (2)
V (Å³)	594.5 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.67
Crystal size (mm)	0.51 × 0.19 × 0.15

Data collection
Diffractometer	Agilent Xcalibur, Atlas, Gemini ultra
Absorption correction	Analytical (CrysAlis PRO; Rigaku OD, 2015 )
T_min, T_max	0.603, 0.822
No. of measured, independent and observed [I > 2σ(I)] reflections	2973, 1377, 1228
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.675

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.094, 0.99
No. of reflections	1373
No. of parameters	74
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.41
Computer programs: CrysAlis PRO (Rigaku OD, 2015), SIR97 (Altomare et al., 1999 ), CRYSTALS (Betteridge et al., 2003 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1517056

Crystal structure: contains datablocks global, New_Global_Publ_Block, I. DOI: https://doi.org/10.1107/S2414314616018204/bh4018sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616018204/bh4018Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616018204/bh4018Isup3.cml

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: Mercury (Macrae et al., 2008); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

4,5-Dichloro-3H-1,2-dithiol-3-one top

Crystal data top

C₃Cl₂OS₂	F(000) = 368
M_r = 187.07	D_x = 2.090 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1441 reflections
a = 8.678 (2) Å	θ = 3.5–28.4°
b = 7.9332 (14) Å	µ = 1.67 mm⁻¹
c = 8.7340 (18) Å	T = 150 K
β = 98.62 (2)°	Plate, light yellow
V = 594.5 (2) Å³	0.51 × 0.19 × 0.15 mm
Z = 4

Data collection top

Agilent Xcalibur, Atlas, Gemini ultra diffractometer	1377 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	1228 reflections with I > 2.0σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 10.4685 pixels mm^-1	θ_max = 28.7°, θ_min = 3.5°
ω scans	h = −6→11
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2015)	k = −10→10
T_min = 0.603, T_max = 0.822	l = −11→11
2973 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	[weight] = 1/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1]T_n-1(x)] where A_i are Chebychev coefficients and x = F /Fmax; w = [weight][1-(deltaF/6*sigmaF)²]² A_i coefficient are: 0.248E + 04 0.417E + 04 0.267E + 04 0.120E + 04 299.
wR(F²) = 0.094	(Δ/σ)_max = 0.0004321
S = 0.99	Δρ_max = 0.45 e Å⁻³
1373 reflections	Δρ_min = −0.41 e Å⁻³
74 parameters	Extinction correction: Larson, Equation 22
0 restraints	Extinction coefficient: 17 (4)
0 constraints

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat 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	0.65286 (6)	0.53082 (7)	0.38502 (6)	0.0173
S2	0.59380 (7)	0.28367 (7)	0.33822 (7)	0.0182
C3	0.4325 (2)	0.3208 (3)	0.1897 (2)	0.0161
C4	0.4052 (2)	0.4996 (3)	0.1666 (2)	0.0145
C5	0.5024 (2)	0.6089 (3)	0.2519 (2)	0.0145
Cl6	0.48670 (7)	0.82139 (7)	0.23385 (7)	0.0207
Cl7	0.25439 (6)	0.56383 (7)	0.03087 (6)	0.0195
O8	0.3614 (2)	0.2041 (2)	0.1230 (2)	0.0232

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0155 (3)	0.0155 (3)	0.0199 (3)	0.00018 (18)	−0.0002 (2)	−0.00018 (19)
S2	0.0196 (3)	0.0133 (3)	0.0210 (3)	0.00319 (19)	0.0008 (2)	0.00174 (19)
C3	0.0178 (10)	0.0132 (10)	0.0175 (10)	0.0016 (8)	0.0032 (8)	−0.0001 (8)
C4	0.0151 (9)	0.0133 (9)	0.0149 (10)	0.0020 (8)	0.0018 (8)	−0.0007 (8)
C5	0.0152 (9)	0.0131 (10)	0.0156 (10)	0.0022 (7)	0.0039 (8)	0.0008 (8)
Cl6	0.0220 (3)	0.0111 (3)	0.0280 (3)	−0.00152 (18)	0.0007 (2)	−0.00077 (19)
Cl7	0.0199 (3)	0.0157 (3)	0.0207 (3)	0.00089 (19)	−0.0038 (2)	0.00105 (19)
O8	0.0283 (9)	0.0126 (8)	0.0270 (9)	−0.0034 (6)	−0.0018 (7)	−0.0025 (6)

Geometric parameters (Å, º) top

S1—S2	2.0521 (8)	C3—O8	1.212 (3)
S1—C5	1.728 (2)	C4—C5	1.353 (3)
S2—C3	1.785 (2)	C4—Cl7	1.707 (2)
C3—C4	1.447 (3)	C5—Cl6	1.696 (2)

S2—S1—C5	93.88 (8)	C3—C4—Cl7	118.83 (17)
S1—S2—C3	97.60 (8)	C5—C4—Cl7	122.75 (18)
S2—C3—C4	110.94 (16)	S1—C5—C4	119.11 (18)
S2—C3—O8	120.71 (17)	S1—C5—Cl6	117.45 (13)
C4—C3—O8	128.3 (2)	C4—C5—Cl6	123.43 (17)
C3—C4—C5	118.4 (2)

Acknowledgements

We are grateful to The Centre National de la Recherche Scientifique (CNRS, France) for the financial support.

References

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