4-Chloro-N-(2,4-dimethyl­phen­yl)benzene­sulfonamide

K Shakuntala; Sabine Foro; B Thimme Gowda

doi:10.1107/S160053681101960X

. 2011 May 28;67(Pt 6):o1536. doi: 10.1107/S160053681101960X

4-Chloro-N-(2,4-dimethylphenyl)benzenesulfonamide

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

PMCID: PMC3120421 PMID: 21754896

Abstract

In the title compound, C₁₄H₁₄ClNO₂S, the N—H bond points away from the dimethylphenyl ring plane. The molecule is twisted at the S atom, with a C—SO₂—NH—C torsion angle of −75.5 (2)°. The two aromatic rings are tilted relative to each other by 63.3 (1)°. The Cl atom on the chlorobenzene ring is disordered over two sites with site-occupation factors of 0.59 (3) and 0.41 (3), respectively. The crystal structure features inversion-related dimers linked by intermolecular N—H⋯O hydrogen bonds.

Related literature

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

Experimental

Crystal data

C₁₄H₁₄ClNO₂S
M _r = 295.77
Monoclinic,
a = 8.0493 (7) Å
b = 11.4980 (9) Å
c = 15.505 (1) Å
β = 90.512 (8)°
V = 1434.94 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 293 K
0.40 × 0.38 × 0.38 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.854, T _max = 0.860
5316 measured reflections
2920 independent reflections
2299 reflections with I > 2σ(I)
R _int = 0.012

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.110
S = 1.04
2920 reflections
188 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.28 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/S160053681101960X/sj5151sup1.cif

e-67-o1536-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681101960X/sj5151Isup2.hkl

e-67-o1536-Isup2.hkl^{(143.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681101960X/sj5151Isup3.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	0.83 (2)	2.24 (2)	3.052 (2)	165 (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 hydrogen bonding preferences of sulfonamides have been investigated (Adsmond & Grant, 2001). As part of our work on the substituent effects in the structures of this class of compounds (Gowda et al., 2004, 2007; Shakuntala et al., 2011a,b,c), the crystal structure of 4-chloro-N-(2,4-dimethylphenyl)-benzenesulfonamide (I) has been determined (Fig.1). In the structure, the amide H atom is trans to one of the O atoms of the SO₂ group. Furthermore, the N—H bond is positioned away from the methyl groups in the aromatic ring.

The molecule is twisted at the S atom with the C—SO₂—NH—C torsion angle of -75.5 (2)°, compared to the values of -70.3 (3)° in 4-chloro-N-(2,3-dimethylphenyl)-benzenesulfonamide (II) (Shakuntala et al., 2011b), -70.0 (2)° in 4-chloro-N- (2,6-dimethylphenyl)-benzenesulfonamide (III)(Shakuntala et al., 2011c), and -53.8 (3)° and -63.4 (3)° in the two independent molecules of 4-chloro-N-(phenyl)-benzenesulfonamide (IV) (Shakuntala et al., 2011a).

The sulfonyl and the anilino benzene rings are tilted relative to each other by 63.3 (1)° in (I), compared to the values of 34.7 (1)° in (II), 31.9 (1)° in (III), and 69.1 (1)° and 82.6 (1)° in the two independent molecules of (IV).

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

Experimental

A 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 2,4-dimethylaniline 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 resulting 4-chloro-N-(2,4-dimethylphenyl)-benzenesulfonamide was filtered under suction and washed thoroughly with cold water. It was then recrystallized to constant melting point from aqueous ethanol The compound was characterized by recording its infrared 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.