4-Chloro-N-(2,6-dimethyl­phen­yl)benzene­sulfonamide

K Shakuntala; Sabine Foro; B Thimme Gowda

doi:10.1107/S160053681101717X

. 2011 May 14;67(Pt 6):o1401. doi: 10.1107/S160053681101717X

4-Chloro-N-(2,6-dimethylphenyl)benzenesulfonamide

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

PMCID: PMC3120512 PMID: 21754786

Abstract

In the title compound, C₁₄H₁₄ClNO₂S, the amido H atom orients itself away from both the ortho-methyl groups in the adjacent aromatic ring. The molecule is twisted at the S atom with an C—SO₂—NH—C torsion angle of −69.9 (2)°. The two aromatic rings are tilted relative to each other by 31.9 (1)°. In the crystal, the molecules are packed into zigzag chains along the b axis via intermolecular 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)methanesulfonamides, see: Gowda et al. (2007 ▶), on the structures of N-(aryl)arylsulfonamides, see: Gowda et al. (2008 ▶); Shakuntala et al. (2011 ▶) and on the oxidative strengths of N-chloro,N-arylsulfonamides, see: Gowda & Kumar (2003 ▶).

Experimental

Crystal data

C₁₄H₁₄ClNO₂S
M _r = 295.77
Orthorhombic,
a = 7.3816 (4) Å
b = 10.2916 (7) Å
c = 18.312 (1) Å
V = 1391.13 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 293 K
0.40 × 0.28 × 0.24 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.850, T _max = 0.906
5356 measured reflections
2767 independent reflections
2255 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.079
S = 1.02
2767 reflections
177 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ▶), 1113 Friedel pairs
Flack parameter: 0.43 (7)

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/S160053681101717X/bq2299sup1.cif

e-67-o1401-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681101717X/bq2299Isup2.hkl

e-67-o1401-Isup2.hkl^{(135.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681101717X/bq2299Isup3.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⋯O1ⁱ	0.82 (2)	2.28 (2)	3.083 (3)	166 (3)

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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 and other aspects of this class of compounds (Gowda et al., 2003, 2007, 2008; Shakuntala et al., 2011), in the present work, the crystal structure of 4-chloro-N-(2,6-dimethylphenyl)-benzenesulfonamide (I) has been determined (Fig.1). In the structure, the amido H atom orients itself away from both the ortho-methyl groups in the adjacent aromatic ring. The molecule is twisted at the S atom with the C—SO₂—NH—C torsion angle of -69.9 (2)°, compared to the values of -53.8 (3)° (molecule 1) and -63.4 (3)° (molecule 2) in 4-chloro-N-(phenyl)-benzenesulfonamide (II) (Shakuntala et al., 2011) and -78.7 (2)° in N-(2,6-dimethylphenyl)-benzenesulfonamide (III) (Gowda et al., 2008)

The sulfonyl and anilino benzene rings in (I) are tilted relative to each other by 31.9 (1)°, compared to the values of 69.1 (1)° in molecule 1 and 82.6 (1)° in molecule 2 of (II), and 44.9 (1)° in (III).

The packing of molecules in (I) into zigzag chains through N—H···O(S) hydrogen bonding (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 2,6-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 resultant 4-chloro-N-(2,6-dimethylphenyl)-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.

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