4-Chloro-N-(3,4-dimethyl­phen­yl)benzene­sulfonamide

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

doi:10.1107/S1600536810015394

. 2010 May 8;66(Pt 6):o1283. doi: 10.1107/S1600536810015394

4-Chloro-N-(3,4-dimethylphenyl)benzenesulfonamide

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

PMCID: PMC2979417 PMID: 21579382

Abstract

In the title compound, C₁₄H₁₄ClNO₂S, the angle between the sulfonyl and aniline benzene rings is 65.5 (1)°. The crystal structure features inversion dimers linked by pairs of N—H⋯O hydrogen bonds. The dimethylphenyl ring is disordered over two different orientations approximately related by a 180° rotation about the C—N bond, with occupancies of 0.643 (6) and 0.357 (6).

Related literature

For the preparation of the title compound, see: Shetty & Gowda (2005 ▶). For our studies of the effect of substituents on the structures of N-(aryl)arylsulfonamides, see: Gowda et al. (2009 ▶, 2010 ▶). For related structures, see: Gelbrich et al. (2007 ▶); Perlovich et al. (2006 ▶).

Experimental

Crystal data

C₁₄H₁₄ClNO₂S
M _r = 295.77
Monoclinic,
a = 13.5000 (9) Å
b = 12.4039 (8) Å
c = 8.7436 (7) Å
β = 104.492 (7)°
V = 1417.55 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 100 K
0.44 × 0.34 × 0.22 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.839, T _max = 0.915
5943 measured reflections
2890 independent reflections
2309 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.107
S = 1.07
2890 reflections
194 parameters
28 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.24 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/S1600536810015394/ci5082sup1.cif

e-66-o1283-sup1.cif^{(19.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015394/ci5082Isup2.hkl

e-66-o1283-Isup2.hkl^{(141.9KB, 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)	2.10 (1)	2.949 (2)	174 (2)

Open in a new tab

Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

As part of a study of substituent effects on the structures of N-(aryl)arylsulfonamides (Gowda et al., 2009, 2010), in the present work, the structure of 4-chloro-N-(3,4-dimethylphenyl)benzenesulfonamide, (I), has been determined (Fig. 1). The N1—C7 bond in the C—SO₂—NH—C segment is gauche [C7—N1—S1—O2 = 64.1 (2)°] with respect to the S1═O1 bond and anti with respect to the S1═O2 bond [C7—N1—S1—O1 = -167.36 (18)°]. The molecule in (I) is bent at the S-atom with a C1—S1—N1—C7 torsion angle of -51.6 (2)°, compared to the value of -61.8 (2)° in 4-methyl-N-(3,4-dimethylphenyl)- benzenesulfonamide (II) (Gowda et al., 2009) and 57.8 (2)° in N-(3,4-dimethylphenyl)benzenesulfonamide (III) (Gowda et al., 2010)

The sulfonyl and the anilino benzene rings in (I) are tilted relative to each other by 65.5 (1)°, compared to the values of 47.8 (1)° in (II) and 65.4 (2)° (disordered sulfonyl ring A) and 57.8 (2)° (disordered sulfonyl ring B) in (III). The remaining bond parameters in (I) are similar to those observed in (II), (III) and other aryl sulfonamides (Perlovich et al., 2006; Gelbrich et al., 2007).

The crystal packing of molecules in (I) through pairs of N—H···O(S) hydrogen bonds (Table 1) is shown in Fig.2.

Experimental

A solution of p-chlorobenzene (10 g) in chloroform (40 ml) was treated dropwise with chlorosulfonic acid (25 ml) at 273 K. 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 3,4-dimethylaniline in the stoichiometric ratio and boiled for 10 min. The reaction mixture was then cooled to room temperature and added to ice cold water (100 ml). The resultant solid 4-chloro-N-(3,4-dimethylphenyl)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 (Shetty & Gowda, 2005). Prism like colourless single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.