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

K Shakuntala; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536811019416

. 2011 May 28;67(Pt 6):o1540. doi: 10.1107/S1600536811019416

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

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

PMCID: PMC3120465 PMID: 21754899

Abstract

In the crystal of the title compound, C₁₃H₁₂ClNO₂S, the N—H bond is anti to the meta-methyl group in the aniline ring. The C—SO₂—NH—C torsion angle is −57.6 (2)°. The sulfonyl and aniline benzene rings are tilted relative to each other by 84.7 (1)°. The crystal structure features inversion-related dimers linked by pairs of N—H⋯O hydrogen bonds.

Related literature

For hydrogen-bonding modes of sulfonamides, see; Adsmond & Grant (2001 ▶). For our study of the effect of substituents on the structures of N-(aryl)-amides, see: Gowda et al. (2004 ▶), on the structures of N-(aryl)arylsulfonamides, see: Gowda et al. (2010 ▶); Nirmala et al. (2009 ▶); Shakuntala et al. (2011 ▶) and on the structures of N-(aryl)methanesulfonamides, see: Gowda et al. (2007 ▶).

Experimental

Crystal data

C₁₃H₁₂ClNO₂S
M _r = 281.75
Monoclinic,
a = 14.202 (1) Å
b = 14.561 (1) Å
c = 13.271 (1) Å
β = 97.292 (9)°
V = 2722.2 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 293 K
0.48 × 0.44 × 0.40 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.821, T _max = 0.848
5706 measured reflections
2777 independent reflections
2186 reflections with I > 2σ(I)
R _int = 0.012

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.119
S = 1.05
2777 reflections
167 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.45 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/S1600536811019416/ds2114sup1.cif

e-67-o1540-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811019416/ds2114Isup2.hkl

e-67-o1540-Isup2.hkl^{(136.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811019416/ds2114Isup3.cml

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⋯O2ⁱ	0.84 (2)	2.11 (2)	2.942 (2)	172 (2)

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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 sulfonamide moieties are the constituents of many biologically important compounds. The hydrogen bonding preferences of sulfonamides has been investigated (Adsmond & Grant, 2001). As a part of studying the substituent effects on the structures of this class of compounds (Gowda et al., 2004, 2007, 2010; Nirmala et al., 2009, Shakuntala et al., 2011), in the present work, the crystal structure of 4-chloro-N-(3-methylphenyl)-benzenesulfonamide (I) has been determined (Fig.1). In the title compound, the N—C bond in the C—SO₂—NH—C segment has gauche torsions with respect to the S═O bonds. Furthermore, the N—H bond is anti to the meta-methyl group in the anilino ring, similar to that observed in 4-methyl-N-(3-methylphenyl)-benzenesulfonamide (II) (Nirmala et al., 2009), but in contrast to the syn conformation observed with respect to the meta-methyl groups in N-(3-methylphenyl)-benzenesulfonamide (III) (Gowda et al., 2010)

The molecule is twisted at the S atom with the C—SO₂—NH—C torsion angle of -57.6 (2)°, compared to the values of 56.7 (3)° in (II), 55.8 (2)° (molecule 1) and -58.4 (3)° (molecule 2) in the two molecules of (III), and -53.8 (3)° and -63.4 (3)° in the two independent molecules of 4-chloro-N-(phenyl)-benzenesulfonamide (IV)(Shakuntala et al., 2011).

The sulfonyl and the anilino benzene rings are tilted relative to each other by 84.7 (1)° in (I), compared to the values of 83.9 (1)° in (II), 67.9 (1)° (molecule 1) and 68.6 (1)° (molecule 2) in (III), and 69.1 (1)° and 82.6 (1)° in the two independent molecules of (IV).

The packing of molecules in the crystal via intermolecular N—H···O hydrogen bonds (Table 1) is shown in Fig. 2.

Experimental

The solution of chlorobenzene (10 ml) in chloroform (40 ml) was treated 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 m-toluidine 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-methylphenyl)-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 recording its infrared and NMR spectra.

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