4-Chloro-2-methyl-N-(2-methyl­phen­yl)­benzene­sulfonamide

B Thimme Gowda; Sabine Foro; P G Nirmala; Hiromitsu Terao; Hartmut Fuess

doi:10.1107/S1600536809009623

. 2009 Mar 19;65(Pt 4):o800. doi: 10.1107/S1600536809009623

4-Chloro-2-methyl-N-(2-methylphenyl)benzenesulfonamide

B Thimme Gowda ^a,^*, Sabine Foro ^b, P G Nirmala ^a, Hiromitsu Terao ^c, Hartmut Fuess ^b

PMCID: PMC2969047 PMID: 21582524

Abstract

In the crystal structure of the title compound, C₁₄H₁₄ClNO₂S, the two aromatic rings are tilted relative to each other by 45.8 (1)°. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds occur.

Related literature

For related structures, see: Gelbrich et al. (2007 ▶); Gowda et al. (2009a ▶,b ▶); Perlovich et al. (2006 ▶).

Experimental

Crystal data

C₁₄H₁₄ClNO₂S
M _r = 295.77
Triclinic,
a = 8.1200 (8) Å
b = 8.1832 (8) Å
c = 10.985 (1) Å
α = 95.81 (1)°
β = 96.92 (1)°
γ = 106.82 (1)°
V = 686.46 (11) Å³
Z = 2
Cu Kα radiation
μ = 3.86 mm⁻¹
T = 299 K
0.50 × 0.48 × 0.18 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.228, T _max = 0.500
2572 measured reflections
2366 independent reflections
2194 reflections with I > 2σ(I)
R _int = 0.054
3 standard reflections frequency: 120 min intensity decay: 2.5%

Refinement

R[F ² > 2σ(F ²)] = 0.072
wR(F ²) = 0.235
S = 1.10
2366 reflections
178 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Data collection: CAD-4-PC (Enraf–Nonius, 1996 ▶); cell refinement: CAD-4-PC; data reduction: REDU4 (Stoe & Cie, 1987 ▶); 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/S1600536809009623/bt2900sup1.cif

e-65-0o800-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009623/bt2900Isup2.hkl

e-65-0o800-Isup2.hkl^{(116.2KB, 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⋯O2ⁱ	0.87 (4)	2.14 (4)	2.993 (4)	167 (3)

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

In the present work, as part of a study of substituent effects on the structures of N-(aryl)-arylsulfonamides, the structure of 4-chloro-2-methyl-N-(2-methylphenyl)benzenesulfonamide has been determined (Gowda et al. 2009a,b). The conformations of the N—C bonds in the C—SO₂—NH—C segment have trans and gauche torsion angles with the S=O bonds (Fig. 1). The molecule is bent at the S atom with the C—SO₂—NH—C torsion angle of 73.0 (2). The ortho-methyl group in the sulfonyl benzene ring is oriented away from the S=O bonds and so also the ortho-methyl group in the anilino benzene ring from the N—H bond. The two benzene rings are tilted relative to each other by 45.8 (1)°, compared with the values of 86.6 (2)° (molecule 1) and 83.0 (2)° (molecule 2), in the two independent molecules of 4-chloro-2-methyl- N-(phenyl)benzenesulfonamide (Gowda et al., 2009a). The other bond parameters in the title compound are similar to those observed in 2,4-dimethyl-N-(phenyl)benzenesulfonamide (Gowda et al., 2009b) and other aryl sulfonamides (Perlovich et al., 2006; Gelbrich et al., 2007). The crystal packing of the molecules is characterized by N—H···O(S) hydrogen bonds (Table 1, Fig.2) .

Experimental

A solution of m-chlorotoluene (10 cc) in chloroform (40 cc) was treated dropwise with chlorosulfonic acid (25 cc) 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-chloro-2-methylbenzenesulfonylchloride was treated with o-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 cc). The resultant solid 4-chloro-2-methyl-N- (2-methylphenyl)benzenesulfonamide was filtered under suction and washed thoroughly with cold water. It was then recrystallized to constant melting point from dilute ethanol. The purity of the compound was checked and characterized by recording its infrared and NMR spectra. The single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.