N-(3,4-Dichloro­phen­yl)-4-methyl­benzene­sulfonamide

K Shakuntala; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536810051305

. 2010 Dec 11;67(Pt 1):o104. doi: 10.1107/S1600536810051305

N-(3,4-Dichlorophenyl)-4-methylbenzenesulfonamide

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

PMCID: PMC3050347 PMID: 21522617

Abstract

In the title compound, C₁₃H₁₁Cl₂NO₂S, 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 64.3 (4)°. Furthermore, the conformation of the N—H bond and the meta-chloro group in the adjacent benzene ring are anti to each other. The two benzene rings are tilted relative to each other by 82.5 (1)°. In the crystal, molecules are linked by pairs of N—H⋯O(S) hydrogen bonds, forming inversion dimers.

Related literature

For our study of the effect of substituents on the structures of N-(aryl)arylsulfonamides, see: Gowda et al. (2009 ▶); Shakuntala et al. (2010 ▶, 2011 ▶); For related structures, see: Gelbrich et al. (2007 ▶); Perlovich et al. (2006 ▶).

Experimental

Crystal data

C₁₃H₁₁Cl₂NO₂S
M _r = 316.19
Monoclinic,
a = 9.543 (1) Å
b = 13.628 (2) Å
c = 10.893 (1) Å
β = 94.85 (1)°
V = 1411.6 (3) Å³
Z = 4
Cu Kα radiation
μ = 5.50 mm⁻¹
T = 299 K
0.40 × 0.28 × 0.18 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.217, T _max = 0.438
2927 measured reflections
2462 independent reflections
1791 reflections with I > 2σ(I)
R _int = 0.117
3 standard reflections every 120 min intensity decay: 1.0%

Refinement

R[F ² > 2σ(F ²)] = 0.086
wR(F ²) = 0.236
S = 1.03
2462 reflections
176 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.97 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/S1600536810051305/ds2077sup1.cif

e-67-0o104-sup1.cif^{(16.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051305/ds2077Isup2.hkl

e-67-0o104-Isup2.hkl^{(121KB, 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	0.83 (3)	2.10 (3)	2.908 (5)	166 (5)

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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

As part of a study of the substituent effects on the crystal structures of N-(aryl)-arylsulfonamides (Gowda et al., 2009; Shakuntala et al., 2010; 2011), in the present work, the structure of N-(3,4-dichlorophenyl)-4-methylbenzenesulfonamide (I) has been determined. In (I), the conformation of the N—C bond in the C—SO₂—NH—C segment has gauche torsions with respect to the S═O bonds (Fig. 1). The conformation of the N—H bond and the meta-chloro groups in the adjacent benzene ring are anti to each other.

The molecule is bent at the S atom with the C—SO₂—NH—C torsion angle of 64.3 (4)°, compared to the values of 65.4 (2)° (molecule 1) and -61.7 (2)° (molecule 2) in N-(2,3-dichlorophenyl)-4- methylbenzenesulfonamide (II) (Shakuntala et al., 2010), 62.1 (2)° in N-(2,5-dichlorophenyl)-4-methylbenzenesulfonamide (III) (Shakuntala et al., 2011) and 69.3 (4)° in N-(3,5-dichlorophenyl)-4-methylbenzenesulfonamide (IV) (Gowda et al., 2009).

The benzene rings in the title compound are tilted relative to each other by 82.5 (1)°, compared to the values of 76.0 (1)° (molecule 1) and 79.9 (1)° (molecule 2) in (II), 67.8 (1)° in (III) and 79.6 (1)° in (IV).

The other bond parameters in (I) are similar to those observed in (II), (III), (IV) and other aryl sulfonamides (Perlovich et al., 2006; Gelbrich et al., 2007).

The packing of molecules linked by of N—H···O(S) hydrogen bonds(Table 1) is shown in Fig. 2.

Experimental

The solution of toluene (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-methylbenzenesulfonylchloride was treated with 3,4-dichloroaniline 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 N-(3,4-dichlorophenyl)-4-methylbenzenesulfonamide 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.

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