5-Anilino-4-chloro-3H-1,2-di­thiol-3-one

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

doi:10.1107/S2414314616017363

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161736

https://doi.org/10.1107/S2414314616017363

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5-Anilino-4-chloro-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 M. Bolte, Goethe-Universität Frankfurt Germany (Received 27 October 2016; accepted 28 October 2016; online 4 November 2016)

In the title compound, C₉H₆ClNOS₂, the two rings subtend a dihedral angle of 51.9 (7)°. The S—S bond has a length of 2.061 (2) Å. In the crystal, hydrogen-bonding interactions and π–π stacking [centroid–centroid distance = 3.927 (2) Å] contacts link the molecules into a three-dimensional network.

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

CCDC reference: 1512930

Structure description

The title compound, C₉H₆ClONS₂, is a derivative of 1,2-dithiole-3-one, a family of bioactive compounds (He et al., 2004 ). It crystallizes from mixture of ethanol and dichloromethane in the monoclinic space group P2₁/n (Fig. 1). The molecule is composed of two rings with a dihedral angle of 51.9 (7)° between them. The length of the S—S bond is 2.061 (2) Å and the angles C9—N8—C3, C3—S2—S1, S2—S1—C5 and C5—C4—C3 are 126.2 (4), 94.5 (2), 96.8 (2) and 120.5 (4)°, respectively.

Figure 1
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 and 3), the three-dimensional molecular packing is sustained by hydrogen-bonding interactions (C10—H101⋯O6ⁱ, N8—H81⋯O6ⁱⁱ with H⋯A lengths of 2.55 and 1.99 Å, respectively; Table 1) and parallel-displaced π–π aromatic-stacking [centroid–centroid distance = 3.927 (2) Å] contacts between successive molecules in the [100] direction.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H101⋯O6ⁱ	0.93	2.50	3.320 (7)	147 (1)
N8—H81⋯O6ⁱⁱ	0.86	1.99	2.794 (7)	155 (2)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
A view along the b axis of the crystal packing. Hydrogen-bonding interactions are shown as dashed blue lines. Centroids are shown as green dots. The centroid–centroid distance is shown as a light-green dashed line.

Figure 3
A view along the a axis of the crystal packing. Displacement ellipsoids drawn at the 50% probability level. Hydrogen-bonding interactions are shown as dashed blue lines.

Synthesis and crystallization

To a methanol solution (50 ml) of 4,5-dichloro-1,2-dithiol-3-one (C₃Cl₂OS₂, 1 g) and NaHCO₃ (0.5 g), 0.6 g of aniline was added. The mixture was stirred for 20 h at room temperature. Then, 100 ml of distilled water was added, and the formed precipitate was filtered and washed 3 times with distilled water and dried. The product was crystallized in an ethyl acetate solution in 80% yield. The recrystallization process was performed from a 1:1 mixture of ethanol and dichloromethane solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₆ClNOS₂
M_r	243.74
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	3.9268 (6), 20.752 (3), 12.3431 (19)
β (°)	99.182 (14)
V (Å³)	992.9 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.77
Crystal size (mm)	0.38 × 0.14 × 0.09

Data collection
Diffractometer	Rigaku Xcalibur Atlas Gemini ultra
Absorption correction	Analytical [CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), based on expressions derived by Clark & Reid (1995 )]
T_min, T_max	0.915, 0.968
No. of measured, independent and observed [I > 2.0σ(I)] reflections	2403, 2403, 1929
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.155, 1.01
No. of reflections	2393
No. of parameters	131
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.79, −1.02
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SIR97 (Altomare et al., 1999 ), CRYSTALS (Betteridge et al., 2003 ), CAMERON (Watkin et al., 1996 ). Weighting scheme: Chebychev polynomial (Watkin, 1994 ; Prince, 1982 ).

Structural data

CCDC reference: 1512930

Crystal structure: contains datablocks global, New_Global_Publ_Block, I. DOI: https://doi.org/10.1107/S2414314616017363/bt4031sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616017363/bt4031Isup2.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

C₉H₆ClNOS₂	F(000) = 496
M_r = 243.74	D_x = 1.630 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2296 reflections
a = 3.9268 (6) Å	θ = 3.6–29.1°
b = 20.752 (3) Å	µ = 0.77 mm⁻¹
c = 12.3431 (19) Å	T = 150 K
β = 99.182 (14)°	Needle, light yellow
V = 992.9 (3) Å³	0.38 × 0.14 × 0.09 mm
Z = 4

Data collection top

Rigaku Xcalibur Atlas Gemini ultra diffractometer	2403 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	1929 reflections with I > 2.0σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 10.4685 pixels mm^-1	θ_max = 29.6°, θ_min = 3.4°
ω scans	h = −5→5
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	k = 0→28
T_min = 0.915, T_max = 0.968	l = 0→15
2403 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)] = 0.066	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.155	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: 0.173E + 04 0.271E + 04 0.145E + 04 406.
S = 1.01	(Δ/σ)_max = 0.001
2393 reflections	Δρ_max = 0.79 e Å⁻³
131 parameters	Δρ_min = −1.02 e Å⁻³
3 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.

Absorption correction: CrysAlisPro 1.171.38.43 (Rigaku OD, 2015) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by Clark and Reid (1995). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Refinement. 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). The hydrogen atom bonded to N was refined with a restraint on the bond length [N8—H81 = 0.82?(2)?Å]. The bond angles C3—N8—H81 and C9—N8—H81 were restrained to be equal with an e.s.d. of 2.0) and the isotropic displacement parameter of H81 was restrained to 1.2Ueq of N8 with an e.s.d of 0.002.

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

	x	y	z	U_iso*/U_eq
S1	0.9772 (3)	0.66331 (5)	0.65293 (9)	0.0245
S2	0.8932 (3)	0.60518 (5)	0.51592 (9)	0.0236
C3	0.6605 (12)	0.6630 (2)	0.4331 (4)	0.0220
C4	0.6087 (12)	0.7208 (2)	0.4813 (4)	0.0212
C5	0.7448 (12)	0.7319 (2)	0.5925 (4)	0.0216
O6	0.7259 (10)	0.78060 (16)	0.6465 (3)	0.0299
Cl7	0.3850 (3)	0.78231 (5)	0.40834 (9)	0.0294
N8	0.5500 (11)	0.64918 (18)	0.3272 (3)	0.0232
C9	0.6041 (13)	0.5905 (2)	0.2735 (3)	0.0218
C10	0.7287 (13)	0.5929 (2)	0.1738 (4)	0.0257
C11	0.7676 (13)	0.5366 (3)	0.1182 (4)	0.0288
C12	0.6940 (14)	0.4775 (2)	0.1607 (4)	0.0290
C13	0.5678 (13)	0.4752 (2)	0.2596 (4)	0.0274
C14	0.5209 (13)	0.5316 (2)	0.3163 (4)	0.0266
H101	0.7838	0.6327	0.1459	0.0308*
H111	0.8502	0.5382	0.0512	0.0351*
H121	0.7281	0.4394	0.1235	0.0353*
H131	0.5129	0.4352	0.2879	0.0330*
H141	0.4324	0.5298	0.3825	0.0320*
H81	0.458 (14)	0.6801 (12)	0.2864 (18)	0.0279*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0318 (6)	0.0215 (5)	0.0180 (5)	0.0009 (5)	−0.0023 (4)	−0.0008 (4)
S2	0.0313 (6)	0.0198 (5)	0.0184 (5)	0.0034 (4)	−0.0001 (4)	−0.0008 (4)
C3	0.025 (2)	0.023 (2)	0.0180 (19)	−0.0024 (18)	0.0046 (16)	0.0000 (16)
C4	0.027 (2)	0.0169 (19)	0.020 (2)	0.0009 (17)	0.0025 (17)	0.0003 (15)
C5	0.027 (2)	0.0182 (18)	0.0195 (19)	−0.0046 (18)	0.0039 (16)	0.0024 (15)
O6	0.043 (2)	0.0218 (16)	0.0222 (16)	0.0002 (15)	−0.0040 (15)	−0.0048 (12)
Cl7	0.0421 (7)	0.0216 (5)	0.0231 (5)	0.0071 (5)	0.0003 (5)	0.0029 (4)
N8	0.036 (2)	0.0176 (16)	0.0144 (16)	0.0023 (16)	−0.0012 (15)	−0.0022 (13)
C9	0.031 (2)	0.0161 (18)	0.0167 (19)	−0.0006 (18)	−0.0023 (16)	−0.0028 (15)
C10	0.031 (2)	0.025 (2)	0.0195 (19)	−0.0011 (19)	−0.0005 (17)	−0.0004 (17)
C11	0.030 (2)	0.036 (3)	0.020 (2)	0.003 (2)	0.0036 (17)	−0.0052 (19)
C12	0.033 (2)	0.023 (2)	0.029 (2)	0.003 (2)	−0.0006 (19)	−0.0103 (18)
C13	0.033 (2)	0.023 (2)	0.025 (2)	0.004 (2)	−0.0014 (18)	−0.0012 (18)
C14	0.032 (2)	0.024 (2)	0.022 (2)	−0.003 (2)	0.0008 (18)	0.0028 (17)

Geometric parameters (Å, º) top

S1—S2	2.0605 (15)	C9—C14	1.391 (6)
S1—C5	1.789 (5)	C10—C11	1.376 (7)
S2—C3	1.738 (5)	C10—H101	0.932
C3—C4	1.367 (6)	C11—C12	1.382 (7)
C3—N8	1.342 (5)	C11—H111	0.936
C4—C5	1.410 (6)	C12—C13	1.390 (7)
C4—Cl7	1.721 (4)	C12—H121	0.934
C5—O6	1.220 (5)	C13—C14	1.391 (6)
N8—C9	1.417 (5)	C13—H131	0.940
N8—H81	0.859 (19)	C14—H141	0.939
C9—C10	1.396 (6)

S2—S1—C5	96.84 (15)	C10—C9—C14	120.1 (4)
S1—S2—C3	94.51 (16)	C9—C10—C11	119.5 (5)
S2—C3—C4	116.8 (3)	C9—C10—H101	119.4
S2—C3—N8	118.9 (3)	C11—C10—H101	121.2
C4—C3—N8	124.3 (4)	C10—C11—C12	121.2 (5)
C3—C4—C5	120.5 (4)	C10—C11—H111	119.4
C3—C4—Cl7	121.5 (3)	C12—C11—H111	119.4
C5—C4—Cl7	118.0 (3)	C11—C12—C13	119.3 (4)
S1—C5—C4	111.4 (3)	C11—C12—H121	120.6
S1—C5—O6	120.2 (3)	C13—C12—H121	120.2
C4—C5—O6	128.4 (4)	C12—C13—C14	120.5 (5)
C3—N8—C9	126.2 (4)	C12—C13—H131	119.4
C3—N8—H81	116.9 (14)	C14—C13—H131	120.1
C9—N8—H81	116.6 (14)	C9—C14—C13	119.4 (4)
N8—C9—C10	118.8 (4)	C9—C14—H141	120.5
N8—C9—C14	121.0 (4)	C13—C14—H141	120.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H101···O6ⁱ	0.93	2.50	3.320 (7)	147 (1)
N8—H81···O6ⁱⁱ	0.86	1.99	2.794 (7)	155 (2)

Symmetry codes: (i) x+1/2, −y+3/2, z−1/2; (ii) x−1/2, −y+3/2, z−1/2.

Acknowledgements

We are grateful to The French National Center for Scientific Research (CNRS) for financial support.

References

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