N-(2,5-Dichloro­phen­yl)-4-methyl­benzene­sulfonamide

K Shakuntala; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536810050270

. 2010 Dec 4;67(Pt 1):o40. doi: 10.1107/S1600536810050270

N-(2,5-Dichlorophenyl)-4-methylbenzenesulfonamide

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

PMCID: PMC3050363 PMID: 21522749

Abstract

In the title compound, C₁₃H₁₁Cl₂NO₂S, the N—C bond in the C—SO₂—NH—C segment has gauche torsion angles with respect to the S=O bonds. The molecule is bent at the S atom with an C—SO₂—NH—C torsion angle of 62.1 (2)°. Furthermore, the conformation of the N—H bond is syn to the ortho-chloro group in the adjacent benzene ring. The benzene rings are tilted by 67.8 (1)° relative to each other. The crystal structure features dimers linked by N—H⋯O hydrogen bonds. An intramolecular N—H⋯Cl hydrogen bond is also observed.

Related literature

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

Experimental

Crystal data

C₁₃H₁₁Cl₂NO₂S
M _r = 316.19
Monoclinic,
a = 9.075 (1) Å
b = 14.232 (2) Å
c = 10.773 (1) Å
β = 90.49 (1)°
V = 1391.3 (3) Å³
Z = 4
Cu Kα radiation
μ = 5.58 mm⁻¹
T = 299 K
0.45 × 0.40 × 0.40 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
3316 measured reflections
2474 independent reflections
2268 reflections with I > 2σ(I)
R _int = 0.053
3 standard reflections every 120 min intensity decay: 0.5%

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.141
S = 1.14
2474 reflections
177 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.43 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/S1600536810050270/bq2259sup1.cif

e-67-00o40-sup1.cif^{(17.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810050270/bq2259Isup2.hkl

e-67-00o40-Isup2.hkl^{(121.6KB, 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 (2)	2.35 (2)	3.163 (3)	161 (3)
N1—H1N⋯Cl1	0.85 (2)	2.51 (3)	2.976 (2)	116 (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

As part of a study of the substituent effects on the crystal structures of N-(aryl)-arylsulfonamides (Gowda et al., 2009; 2010a, b), in the present work, the structure of 4-methyl-N-(2,5-dichlorophenyl)- benzenesulfonamide (I) has been determined. The conformation of the N—C bond in the C—SO₂—NH—C segment of the structure has gauche torsions with respect to the S═O bonds (Fig. 1). The molecule is bent at the S atoms with the C—SO₂—NH—C torsion angle of 62.1 (2)°, compared to the values of -61.0 (2)° in 4-methyl-N- (2,5-dimethylphenyl)-benzenesulfonamide (II) (Gowda et al., 2010a), -51.6 (3)° in 4-Methyl-N-(phenyl)-benzenesulfonamide (III) (Gowda et al., 2009) and 66.4 (2)° in N-(2,5-dichlorophenyl)-benzenesulfonamide (IV) (Gowda et al., 2010b).

The conformation of the N—H bond is syn to the ortho-chloro group in the adjacent benzene ring.The benzene rings in the title compound are tilted relative to each other by 67.8 (1)°, compared to the values of 49.4 (1)° in (II), 68.4 (1)° in (III) and 73.3 (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).

An intramolecular N—H···Cl hydrogen bond is observed. The crystal packing of molecules in (I) via 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 2,5-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 4-methyl-N-(2,5-dichlorophenyl)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 prism like light brown single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.