1-Chloro­methyl­sulfinyl-2-nitro­benzene

Benmebarek, S.; Boudraa, M.; Bouacida, S.; Daran, J.-C.

doi:10.1107/S1600536812043553

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3207

doi:10.1107/S1600536812043553

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1-Chloromethylsulfinyl-2-nitrobenzene

Sabrina Benmebarek,^a Mhamed Boudraa,^a Sofiane Bouacida ^a,^b ^* and Jean-Claude Daran ^c

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire, Structurale (CHEMS), Université Mentouri-Constantine, 25000 Algeria, ^bDépartement Sciences de la Matière, Faculté des Sciences Exactes et Sciences de la Nature et de la Vie, Université Oum El Bouaghi, Algeria, and ^cLaboratoire de Chimie de Coordination, UPR CNRS 8241, 205 route de Narbonne, 31077 Toulouse Cedex, France
^*Correspondence e-mail: bouacida_sofiane@yahoo.fr

(Received 13 October 2012; accepted 20 October 2012; online 27 October 2012)

In the title compound, C₇H₆ClNO₃S, the nitro group forms a dihedral angle of 2.7 (4)° with the benzene ring. The bond-angle sum at the S atom is 303.7°. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds, forming layers lying parallel to (-101).

Related literature

For the biological and pharmacological activity of sulfoxides, see, for example: Melzig et al. (2009 ); Huang et al. (2010 ). For related structures, see: Yan (2010 ); Kobayashi et al. (2003 ).

Experimental

Crystal data

C₇H₆ClNO₃S
M_r = 219.65
Monoclinic, P 2₁ /c
a = 12.2394 (5) Å
b = 5.5009 (2) Å
c = 14.5537 (11) Å
β = 116.631 (4)°
V = 875.92 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.65 mm⁻¹
T = 180 K
0.23 × 0.20 × 0.18 mm

Data collection

Agilent Xcalibur (Eos, Gemini ultra) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.900, T_max = 1.000
10209 measured reflections
2172 independent reflections
1799 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.071
S = 1.05
2172 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O12ⁱ	0.95	2.44	3.384 (2)	173
C7—H7A⋯O1ⁱⁱ	0.99	2.36	3.2478 (18)	149
C7—H7B⋯O1ⁱⁱⁱ	0.99	2.50	3.332 (2)	142
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) x, y-1, z.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and DIAMOND (Brandenburg & Berndt, 2001 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812043553/hb6974sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043553/hb6974Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812043553/hb6974Isup3.cml

checkCIF report

Comment top

The use of sulfoxides as pharmaceutical has shown promise in recent years (e.g. Melzig et al., 2009 and Huang et al. 2010). As part of our ongoing studies on the synthesis, structures and biological activity of organometallic sulfanilamide complexes we have synthesized and determined the crystal structure of the title compound (I). The molecular geometry and the atom-numbering scheme are shown in Fig 1. In the crystal structure of the title compound, there are two pairs of molecules enantiomers in the unit cell. In each molecule, the nitro group forms a dihedral angle of 2.7 (4)° with the phenyl ring very different to that found in 2-(methylsulfinyl)benzamide (25.6°) (Yan, 2010) and in benzamide (26.31°) (Kobayashi et al., 2003). The crystal packing is stabilized by weak C—H···O hydrogen bonds (Fig. 2) forming non-interacting layers parallel to (-101) planes.

Related literature top

For the biological and pharmacological activity of sulfoxides, see, for example: Melzig et al. (2009); Huang et al. (2010). For related structures, see: Yan (2010); Kobayashi et al. (2003).

Experimental top

O-chloronitrobenzene (1.60 g, 10 mmol) and thioacetic acid (0.80 g, 10 mmol) were dissolved in 75 ml aqua ethanol solution (25 ml water + 50 ml ethanol) and refluxed for 3 h under continuous stirring. Then the obtained product was evaporated at room temperature to dryness. The residue was diluted in 50 ml pure ethanol. After few days, orange bocks were recovered, as the solvent slowly evaporated.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Drawing of asymetric unit of, (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Diagram packing of (I) viwed via b axis showing alterning layers parallel to (-101) planes.

1-Chloromethylsulfinyl-2-nitrobenzene top

Crystal data top

C₇H₆ClNO₃S	F(000) = 448
M_r = 219.65	D_x = 1.666 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6334 reflections
a = 12.2394 (5) Å	θ = 3.3–29.2°
b = 5.5009 (2) Å	µ = 0.65 mm⁻¹
c = 14.5537 (11) Å	T = 180 K
β = 116.631 (4)°	Block, orange
V = 875.92 (9) Å³	0.23 × 0.20 × 0.18 mm
Z = 4

Data collection top

Agilent Xcalibur (Eos, Gemini ultra) diffractometer	2172 independent reflections
Graphite monochromator	1799 reflections with I > 2σ(I)
Detector resolution: 16.1978 pixels mm^-1	R_int = 0.024
ω scans	θ_max = 29.2°, θ_min = 3.7°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	h = −16→15
T_min = 0.900, T_max = 1.000	k = −7→7
10209 measured reflections	l = −19→19

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0401P)² + 0.1537P] where P = (F_o² + 2F_c²)/3
2172 reflections	(Δ/σ)_max = 0.002
118 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₇H₆ClNO₃S	V = 875.92 (9) Å³
M_r = 219.65	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.2394 (5) Å	µ = 0.65 mm⁻¹
b = 5.5009 (2) Å	T = 180 K
c = 14.5537 (11) Å	0.23 × 0.20 × 0.18 mm
β = 116.631 (4)°

Data collection top

Agilent Xcalibur (Eos, Gemini ultra) diffractometer	2172 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1799 reflections with I > 2σ(I)
T_min = 0.900, T_max = 1.000	R_int = 0.024
10209 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.071	H-atom parameters constrained
S = 1.05	Δρ_max = 0.35 e Å⁻³
2172 reflections	Δρ_min = −0.31 e Å⁻³
118 parameters

Special details top

Experimental. Absorption correction: Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. CrysAlisPro (Agilent, 2011)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Cl1	1.06418 (4)	0.73513 (8)	0.59930 (3)	0.03956 (13)
S1	0.81710 (3)	0.81595 (6)	0.57165 (3)	0.02049 (10)
O1	0.85724 (9)	1.04534 (18)	0.63222 (8)	0.0286 (2)
O11	0.71137 (9)	0.42553 (19)	0.45234 (7)	0.0271 (2)
O12	0.58622 (10)	0.15605 (19)	0.45752 (8)	0.0312 (3)
N1	0.65255 (10)	0.3330 (2)	0.49290 (9)	0.0204 (2)
C1	0.73727 (13)	0.7493 (3)	0.71720 (11)	0.0256 (3)
H1	0.7829	0.8934	0.7453	0.031*
C2	0.67575 (14)	0.6385 (3)	0.76600 (11)	0.0298 (3)
H2	0.6802	0.7065	0.8276	0.036*
C3	0.60801 (13)	0.4300 (3)	0.72587 (11)	0.0290 (3)
H3	0.5672	0.354	0.7604	0.035*
C4	0.59970 (12)	0.3319 (3)	0.63530 (11)	0.0238 (3)
H4	0.5518	0.1908	0.6063	0.029*
C5	0.66235 (12)	0.4428 (2)	0.58775 (10)	0.0186 (3)
C6	0.73266 (11)	0.6514 (2)	0.62775 (10)	0.0188 (3)
C7	0.94884 (12)	0.6136 (3)	0.62770 (11)	0.0231 (3)
H7A	0.9786	0.6027	0.703	0.028*
H7B	0.926	0.4484	0.5982	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0267 (2)	0.0429 (3)	0.0519 (3)	−0.00401 (16)	0.02018 (18)	0.00852 (19)
S1	0.02044 (17)	0.01600 (17)	0.02053 (17)	−0.00089 (12)	0.00517 (13)	0.00213 (13)
O1	0.0302 (5)	0.0156 (5)	0.0326 (5)	−0.0035 (4)	0.0074 (5)	−0.0018 (4)
O11	0.0317 (5)	0.0286 (6)	0.0247 (5)	−0.0052 (4)	0.0161 (4)	−0.0025 (4)
O12	0.0313 (6)	0.0277 (6)	0.0311 (6)	−0.0120 (4)	0.0109 (5)	−0.0111 (5)
N1	0.0192 (5)	0.0183 (6)	0.0205 (5)	0.0001 (4)	0.0061 (5)	−0.0008 (4)
C1	0.0237 (7)	0.0241 (7)	0.0235 (7)	0.0014 (6)	0.0057 (6)	−0.0049 (6)
C2	0.0300 (8)	0.0382 (9)	0.0207 (7)	0.0071 (6)	0.0110 (6)	−0.0023 (6)
C3	0.0263 (7)	0.0370 (9)	0.0270 (7)	0.0044 (6)	0.0148 (6)	0.0079 (7)
C4	0.0210 (7)	0.0228 (7)	0.0271 (7)	0.0004 (5)	0.0103 (6)	0.0032 (6)
C5	0.0171 (6)	0.0184 (6)	0.0178 (6)	0.0033 (5)	0.0054 (5)	0.0006 (5)
C6	0.0177 (6)	0.0171 (6)	0.0192 (6)	0.0033 (5)	0.0061 (5)	0.0022 (5)
C7	0.0191 (6)	0.0206 (6)	0.0279 (7)	0.0001 (5)	0.0091 (5)	0.0043 (6)

Geometric parameters (Å, º) top

Cl1—C7	1.7703 (14)	C2—C3	1.382 (2)
S1—O1	1.4908 (10)	C2—H2	0.95
S1—C6	1.8196 (14)	C3—C4	1.385 (2)
S1—C7	1.8236 (14)	C3—H3	0.95
O11—N1	1.2276 (15)	C4—C5	1.3837 (19)
O12—N1	1.2234 (15)	C4—H4	0.95
N1—C5	1.4618 (17)	C5—C6	1.3953 (18)
C1—C2	1.386 (2)	C7—H7A	0.99
C1—C6	1.3865 (19)	C7—H7B	0.99
C1—H1	0.95

O1—S1—C6	104.99 (6)	C5—C4—C3	118.91 (13)
O1—S1—C7	105.15 (6)	C5—C4—H4	120.5
C6—S1—C7	93.53 (6)	C3—C4—H4	120.5
O12—N1—O11	123.31 (12)	C4—C5—C6	122.02 (12)
O12—N1—C5	118.97 (11)	C4—C5—N1	117.44 (12)
O11—N1—C5	117.72 (11)	C6—C5—N1	120.53 (12)
C2—C1—C6	120.49 (14)	C1—C6—C5	117.97 (13)
C2—C1—H1	119.8	C1—C6—S1	115.84 (11)
C6—C1—H1	119.8	C5—C6—S1	126.16 (10)
C3—C2—C1	120.60 (13)	Cl1—C7—S1	107.62 (7)
C3—C2—H2	119.7	Cl1—C7—H7A	110.2
C1—C2—H2	119.7	S1—C7—H7A	110.2
C2—C3—C4	119.97 (13)	Cl1—C7—H7B	110.2
C2—C3—H3	120	S1—C7—H7B	110.2
C4—C3—H3	120	H7A—C7—H7B	108.5

C6—C1—C2—C3	−0.6 (2)	C4—C5—C6—C1	−0.9 (2)
C1—C2—C3—C4	−0.9 (2)	N1—C5—C6—C1	179.16 (12)
C2—C3—C4—C5	1.5 (2)	C4—C5—C6—S1	−179.03 (10)
C3—C4—C5—C6	−0.6 (2)	N1—C5—C6—S1	1.02 (18)
C3—C4—C5—N1	179.38 (12)	O1—S1—C6—C1	−8.09 (12)
O12—N1—C5—C4	3.01 (18)	C7—S1—C6—C1	98.62 (11)
O11—N1—C5—C4	−177.48 (12)	O1—S1—C6—C5	170.09 (11)
O12—N1—C5—C6	−177.04 (12)	C7—S1—C6—C5	−83.20 (12)
O11—N1—C5—C6	2.47 (18)	O1—S1—C7—Cl1	−67.86 (9)
C2—C1—C6—C5	1.4 (2)	C6—S1—C7—Cl1	−174.44 (8)
C2—C1—C6—S1	179.78 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O12ⁱ	0.95	2.44	3.384 (2)	173
C7—H7A···O1ⁱⁱ	0.99	2.36	3.2478 (18)	149
C7—H7B···O1ⁱⁱⁱ	0.99	2.50	3.332 (2)	142

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

Experimental details

Crystal data
Chemical formula	C₇H₆ClNO₃S
M_r	219.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	180
a, b, c (Å)	12.2394 (5), 5.5009 (2), 14.5537 (11)
β (°)	116.631 (4)
V (Å³)	875.92 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.65
Crystal size (mm)	0.23 × 0.20 × 0.18

Data collection
Diffractometer	Agilent Xcalibur (Eos, Gemini ultra) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.900, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10209, 2172, 1799
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.071, 1.05
No. of reflections	2172
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.31

Computer programs: CrysAlis PRO (Agilent, 2011), SIR2002 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Berndt, 2001), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O12ⁱ	0.95	2.44	3.384 (2)	173
C7—H7A···O1ⁱⁱ	0.99	2.36	3.2478 (18)	149
C7—H7B···O1ⁱⁱⁱ	0.99	2.50	3.332 (2)	142

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

Acknowledgements

This work was supported by the Unité de Recherche de Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Université Mentouri-Constantine, Algeria. Thanks are due to MESRS (Ministére de l'Enseignement Supérieur et de la Recherche Scientifique and ANDRU (l'Agence Nationale pour le Développement de la Recherche Universitaire) for financial support via the PNR programm.

References

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