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ISSN: 2414-3146

4,5-Di­chloro-3H-1,2-di­thiol-3-one

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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.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

The title compound belongs to a family of bioactive compounds (He et al., 2004[He, X., Reeve, A. M. E., Desai, U. R., Kellogg, G. E. & Reynolds, K. A. (2004). Antimicrob. Agents Chemother. 48, 3093-3102.]). Its crystallization from an ethyl acetate solution leads to a monoclinic system with P21/n space group (Figs. 1[link] and 2[link]). 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]
Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
[Figure 2]
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[link]).

[Figure 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[link].

Table 1
Experimental details

Crystal data
Chemical formula C3Cl2OS2
Mr 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)
V3) 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[Rigaku OD (2015). CrysAlis PRO. Rigaku Americas Corporation, The Woodlands, Texas, USA.])
Tmin, Tmax 0.603, 0.822
No. of measured, independent and observed [I > 2σ(I)] reflections 2973, 1377, 1228
Rint 0.036
(sin θ/λ)max−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
Δρmax, Δρmin (e Å−3) 0.45, −0.41
Computer programs: CrysAlis PRO (Rigaku OD, 2015[Rigaku OD (2015). CrysAlis PRO. Rigaku Americas Corporation, The Woodlands, Texas, USA.]), SIR97 (Altomare et al., 1999[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.]), CRYSTALS (Betteridge et al., 2003[Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]).

Structural data


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
C3Cl2OS2F(000) = 368
Mr = 187.07Dx = 2.090 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1441 reflections
a = 8.678 (2) Åθ = 3.5–28.4°
b = 7.9332 (14) ŵ = 1.67 mm1
c = 8.7340 (18) ÅT = 150 K
β = 98.62 (2)°Plate, light yellow
V = 594.5 (2) Å30.51 × 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 Source1228 reflections with I > 2.0σ(I)
Graphite monochromatorRint = 0.036
Detector resolution: 10.4685 pixels mm-1θmax = 28.7°, θmin = 3.5°
ω scansh = 611
Absorption correction: analytical
(CrysAlis PRO; Rigaku OD, 2015)
k = 1010
Tmin = 0.603, Tmax = 0.822l = 1111
2973 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032 [weight] = 1/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)]
where Ai are Chebychev coefficients and x = F /Fmax; w = [weight]*[1-(deltaF/6*sigmaF)2]2 Ai 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 = 0.99Δρmax = 0.45 e Å3
1373 reflectionsΔρmin = 0.41 e Å3
74 parametersExtinction correction: Larson, Equation 22
0 restraintsExtinction 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
xyzUiso*/Ueq
S10.65286 (6)0.53082 (7)0.38502 (6)0.0173
S20.59380 (7)0.28367 (7)0.33822 (7)0.0182
C30.4325 (2)0.3208 (3)0.1897 (2)0.0161
C40.4052 (2)0.4996 (3)0.1666 (2)0.0145
C50.5024 (2)0.6089 (3)0.2519 (2)0.0145
Cl60.48670 (7)0.82139 (7)0.23385 (7)0.0207
Cl70.25439 (6)0.56383 (7)0.03087 (6)0.0195
O80.3614 (2)0.2041 (2)0.1230 (2)0.0232
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0155 (3)0.0155 (3)0.0199 (3)0.00018 (18)0.0002 (2)0.00018 (19)
S20.0196 (3)0.0133 (3)0.0210 (3)0.00319 (19)0.0008 (2)0.00174 (19)
C30.0178 (10)0.0132 (10)0.0175 (10)0.0016 (8)0.0032 (8)0.0001 (8)
C40.0151 (9)0.0133 (9)0.0149 (10)0.0020 (8)0.0018 (8)0.0007 (8)
C50.0152 (9)0.0131 (10)0.0156 (10)0.0022 (7)0.0039 (8)0.0008 (8)
Cl60.0220 (3)0.0111 (3)0.0280 (3)0.00152 (18)0.0007 (2)0.00077 (19)
Cl70.0199 (3)0.0157 (3)0.0207 (3)0.00089 (19)0.0038 (2)0.00105 (19)
O80.0283 (9)0.0126 (8)0.0270 (9)0.0034 (6)0.0018 (7)0.0025 (6)
Geometric parameters (Å, º) top
S1—S22.0521 (8)C3—O81.212 (3)
S1—C51.728 (2)C4—C51.353 (3)
S2—C31.785 (2)C4—Cl71.707 (2)
C3—C41.447 (3)C5—Cl61.696 (2)
S2—S1—C593.88 (8)C3—C4—Cl7118.83 (17)
S1—S2—C397.60 (8)C5—C4—Cl7122.75 (18)
S2—C3—C4110.94 (16)S1—C5—C4119.11 (18)
S2—C3—O8120.71 (17)S1—C5—Cl6117.45 (13)
C4—C3—O8128.3 (2)C4—C5—Cl6123.43 (17)
C3—C4—C5118.4 (2)
 

Acknowledgements

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

References

First citationAltomare, 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
First citationBetteridge, 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
First citationHe, X., Reeve, A. M. E., Desai, U. R., Kellogg, G. E. & Reynolds, K. A. (2004). Antimicrob. Agents Chemother. 48, 3093–3102.  Web of Science CrossRef PubMed CAS Google Scholar
First citationMacrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationRigaku OD (2015). CrysAlis PRO. Rigaku Americas Corporation, The Woodlands, Texas, USA.  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.

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