4-Chloro-N-(3-chloro­phen­yl)benzene­sulfonamide

K Shakuntala; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536811011366

. 2011 Mar 31;67(Pt 4):o1017. doi: 10.1107/S1600536811011366

4-Chloro-N-(3-chlorophenyl)benzenesulfonamide

K Shakuntala ^a, Sabine Foro ^b, B Thimme Gowda ^a,^*

PMCID: PMC3099951 PMID: 21754033

Abstract

In the crystal of the title compound, C₁₂H₉Cl₂NO₂S, the molecule is twisted at the S atom with a C—SO₂—NH—C torsion angle of −58.4 (3)°. Furthermore, the N—H bond in this segment is anti to the meta-chloro group. The dihedral angle between the aromatic rings is 77.1 (1)°. The crystal structure features inversion-related dimers linked by N—H⋯O hydrogen bonds.

Related literature

For our study on the effect of substituents on the structures of N-(aryl)arylsulfonamides, see: Gowda et al. (2005 ▶); Shakuntala et al. (2011 ▶). For the effect of substituents on the oxidative strengths of N-chloro,N-arylsulfonamides, see: Gowda & Shetty (2004 ▶) and for the effect of substituents on the NQR spectra of N-(aryl)-amides, see: Gowda et al. (2000 ▶).

Experimental

Crystal data

C₁₂H₉Cl₂NO₂S
M _r = 302.16
Monoclinic,
a = 9.378 (2) Å
b = 13.478 (3) Å
c = 10.251 (2) Å
β = 90.48°
V = 1295.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.65 mm⁻¹
T = 293 K
0.48 × 0.44 × 0.44 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.745, T _max = 0.762
4232 measured reflections
2115 independent reflections
1572 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.129
S = 1.08
2115 reflections
166 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011366/ds2101sup1.cif

e-67-o1017-sup1.cif^{(16.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011366/ds2101Isup2.hkl

e-67-o1017-Isup2.hkl^{(104KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.85 (2)	2.09 (2)	2.939 (4)	176 (4)

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Symmetry code: (i) Inline graphic .

Acknowledgments

KS thanks the University Grants Commission, Government of India, New Delhi, for the award of a research fellowship under its faculty improvement program.

supplementary crystallographic information

Comment

The amide and sulfonamide moieties are important constituents of many biologically important compounds. As a part of studying the substituent effects on the structures and other aspects of this class of compounds (Gowda et al., 2000, 2004, 2005; Shakuntala et al., 2011), in the present work, the crystal structure of 4-chloro-N-(3-chlorophenyl)benzenesulfonamide (I) has been determined (Fig. 1). The molecule is bent at the S atom with the C—SO₂—NH—C torsion angle of -58.4 (3)°, compared to the value of -56.7 (2)° in 4-chloro-N-(2,3-dichlorophenyl)-benzenesulfonamide (II) (Shakuntala et al., 2011). The N—H bond and the meta- chloro group in the anilino benzene ring are anti to each other.

The sulfonyl and the anilino benzene rings in (I) are tilted relative to each other by 77.1 (1)°, compared to the value of 56.5 (1)° in (II).

Inermolecular N—H···O(S) hydrogen bonding interactions generates inversion related dimers which are further packed via van der Waals interactions in the crystal structure (Fig.2).

Experimental

The solution of chlorobenzene (10 ml) in chloroform (40 ml) was added dropwise with chlorosulfonic acid (25 ml) at 0 ° C. After the initial evolution of hydrogen chloride subsided, the reaction mixture was brought to room temperature and poured into crushed ice in a beaker. The chloroform layer was separated, washed with cold water and allowed to evaporate slowly. The residual 4-chlorobenzenesulfonylchloride was treated with 3-chloroaniline in the stoichiometric ratio and boiled for ten minutes. The reaction mixture was then cooled to room temperature and added to ice cold water (100 ml). The resultant 4-chloro-N-(3-chlorophenyl)-benzenesulfonamide was filtered under suction and washed thoroughly with cold water. It was then recrystallized to constant melting point from dilute ethanol. The compound was characterized by FT-IR and NMR spectra.

Prism like colorless single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.