N-(2-Chloro­phen­yl)-2,4-dimethyl­benzene­sulfonamide

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

doi:10.1107/S1600536810015916

. 2010 May 8;66(Pt 6):o1282. doi: 10.1107/S1600536810015916

N-(2-Chlorophenyl)-2,4-dimethylbenzenesulfonamide

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

PMCID: PMC2979443 PMID: 21579381

Abstract

In the title compound, C₁₄H₁₄ClNO₂S, the conformation of the N—C bond in the C—SO₂—NH—C segment has gauche torsions with respect to the S=O bonds. The molecule is bent at the S atom with a C—SO₂—NH—C torsion angle of −54.9 (2)°. The sulfonyl and aniline benzene rings are rotated relative to each other by 75.7 (1)°. An intramolecular N—H⋯Cl hydrogen bond is present. In the crystal, intermolecular N—H⋯O hydrogen-bonding interactions are observed and the molecules are packed into chains parallel to the b axis.

Related literature

For the preparation of the title compound, see: Savitha & Gowda (2006 ▶). For related structures, see: Gelbrich et al. (2007 ▶); Gowda et al. (2009a ▶,b ▶, 2010 ▶); Nirmala et al. (2009 ▶); Perlovich et al. (2006 ▶).

Experimental

Crystal data

C₁₄H₁₄ClNO₂S
M _r = 295.77
Orthorhombic,
a = 10.574 (1) Å
b = 16.269 (2) Å
c = 16.859 (2) Å
V = 2900.2 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 299 K
0.38 × 0.34 × 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 = 0.862, T _max = 0.909
18999 measured reflections
2922 independent reflections
2330 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.102
S = 1.05
2922 reflections
178 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.27 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/S1600536810015916/rz2441sup1.cif

e-66-o1282-sup1.cif^{(18.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015916/rz2441Isup2.hkl

e-66-o1282-Isup2.hkl^{(143.5KB, 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 (1)	2.20 (1)	3.010 (2)	159 (2)
N1—H1N⋯Cl1	0.85 (1)	2.63 (2)	2.9822 (18)	106 (2)

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

As part of a study of the substituent effects on the structures of N-(aryl)-arylsulfonamides (Gowda et al. , 2009a,b, 2010), in the present work the structure of 2,4-dimethyl-N-(2-chlorophenyl)benzenesulfonamide (I) has been determined (Fig. 1). The conformation of the N—C bond in the C—SO₂—NH—C segment has gauche torsions with respect to the S═O bonds. The molecule is bent at the S atom with the C1—SO₂—NH—C7 torsion angle of -54.9 (2)°, compared to the values of 71.6 (1)° in 2,4-dimethyl-N-(2-methylphenyl)benzenesulfonamide (II) (Nirmala et al., 2009), 74.8 (4)° in 4-chloro-2-methyl-N-(2-chlorophenyl)benzenesulfonamide (III) (Gowda et al., 2009b), -46.1 (3)° (molecule 1) and 47.7 (3)° (molecule 2) in the two molecules of 2,4-dimethyl-N-(phenyl)benzenesulfonamide (IV) (Gowda et al., 2009a) and -54.8 (2)° in N-(2-chlorophenyl)-4-methylbenzenesulfonamide (V) (Gowda et al., 2010).

The two benzene rings in (I) are tilted relative to each other by 75.7 (1)°, compared to the values of 47.0 (1)° (II), 45.5 (2)° in (III), 67.5 (1)° in molecule 1 and 72.9 (1)° in molecule 2 of (IV), and 71.6 (1)° in (V). The other bond parameters in (I) are similar to those observed in (II), (III), (IV), (V) and other aryl sulfonamides (Perlovich et al., 2006; Gelbrich et al., 2007).

The structure shows simultaneous N—H···Cl intramolecular and N—H···O intermolecular H-bonding (Table 1). The crystal packing of molecules in (I) via N—H···O(S) hydrogen bonds is shown in Fig.2.

Experimental

A solution of 1,3-xylene (1,3-dimethylbenzene) (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 2,4-dimethylbenzenesulfonylchloride was treated with 2-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 cc). The resultant solid 2,4-dimethyl-N-(2-chlorophenyl)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 (Savitha & Gowda, 2006). The prism like colourless single crystals used in X-ray diffraction studies were grown by slow evaporation of an ethanol solution at room temperature.