N-(3,4-Dichloro­phen­yl)-2,4-dimethyl­benzene­sulfonamide

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

doi:10.1107/S1600536809028840

. 2009 Jul 25;65(Pt 8):o1976. doi: 10.1107/S1600536809028840

N-(3,4-Dichlorophenyl)-2,4-dimethylbenzenesulfonamide

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

PMCID: PMC2977482 PMID: 21583652

Abstract

In the crystal structure of the title compound, C₁₄H₁₃Cl₂NO₂S, the configurations of the N—C bond with respect to the S=O bonds are trans and gauche. The molecule is bent at the S atom with a C—SO₂—NH—C torsion angle of −69.7 (2)°. The conformation of the N—H bond is syn to the 3-chloro group in the substituted aniline ring. The two benzene rings are tilted with respect to each other by 82.4 (1)°. The presence of N—H⋯O(S) hydrogen bonding packs the molecules into supramolecular chains along the b axis.

Related literature

For our study of the effect of substituents on the structures of N-(aryl)-arylsulfonamides, see: Gowda et al. (2008 ▶; 2009a ▶,b ▶). For related structures, see: Gelbrich et al. (2007 ▶); Perlovich et al. (2006 ▶).

Experimental

Crystal data

C₁₄H₁₃Cl₂NO₂S
M _r = 330.21
Monoclinic,
a = 8.8046 (7) Å
b = 9.2688 (8) Å
c = 18.947 (1) Å
β = 99.644 (8)°
V = 1524.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.56 mm⁻¹
T = 299 K
0.44 × 0.40 × 0.38 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.790, T _max = 0.815
10274 measured reflections
3064 independent reflections
2618 reflections with I > 2σ(I)
R _int = 0.013

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.100
S = 1.05
3064 reflections
186 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.39 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/S1600536809028840/tk2510sup1.cif

e-65-o1976-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028840/tk2510Isup2.hkl

e-65-o1976-Isup2.hkl^{(150.4KB, 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	0.833 (16)	2.176 (17)	2.984 (2)	164 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for extensions of his research fellowship.

supplementary crystallographic information

Comment

As part of a study of substituent effects on the structures of N-(aryl)-arylsulfonamides (Gowda et al., 2008, 2009a, b), in the present work, the structure of 2,4-dimethyl-N-(3,4-dichlorophenyl)benzenesulfonamide (I) has been determined. The conformations of the N—C bond in the C—SO₂—NH—C segment are trans and gauche to the S=O bonds (Fig. 1). The molecule is bent at the S atom with the C—SO₂—NH—C torsion angle of -69.7 (2)°, compared to the values of -48.2 (2)° in 2,4-dichloro-N-(3,4-dichlorophenyl)benzenesulfonamide (II) (Gowda et al., 2009b), and 46.1 (3)° and 47.7 (3)° in the two independent molecules of 2,4-dimethyl-N-(phenyl)benzenesulfonamide (III) (Gowda et al., 2009a). The conformation of the N—H bond is syn to the meta-chloro group in the substituted aniline ring. The two benzene rings in (I) are tilted by 82.4 (1)° to each other compared to the values of 68.9 (1)° in II, and 67.5 (1)° and 72.9 (1)° in III. The other bond parameters in (I) are similar to those observed in II, III, and other aryl sulfonamides (Gowda et al., 2008; Perlovich et al., 2006; Gelbrich et al., 2007). The crystal packing of molecules in (I) is via N—H···O(S) hydrogen bonding (Table 1) leading to a supramolecular chain.

Experimental

A solution of 1,3-xylene (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 3,4-dichloroaniline in a 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 solid, 2,4-dimethyl-N-(3,4-dichlorophenyl)benzenesulfonamide, was filtered under suction and washed thoroughly with cold water. It was then recrystallized to constant melting point from dilute ethanol. The prisms used in the X-ray analysis were grown in ethanolic solution by a slow evaporation at room temperature.