2,4-Dichloro-N-(3,5-dimethyl­phen­yl)benzene­sulfonamide

Vinola Z Rodrigues; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536811040189

. 2011 Oct 5;67(Pt 11):o2842. doi: 10.1107/S1600536811040189

2,4-Dichloro-N-(3,5-dimethylphenyl)benzenesulfonamide

Vinola Z Rodrigues ^a, Sabine Foro ^b, B Thimme Gowda ^a,^*

PMCID: PMC3247580 PMID: 22219885

Abstract

In the crystal of the title compound, C₁₄H₁₃Cl₂NO₂S, the N—H bond in the C—SO₂—NH—C segment is syn to one of the meta-methyl groups in the aniline benzene ring and anti to the other. Further, the conformation of the N—C bond in the C—SO₂—NH—C segment is gauche with respect to the S=O bonds. The C—SO₂—NH—C torsion angle is 54.9 (2)°. The sulfonyl and aniline benzene rings are tilted relative to each other by 82.8 (1)°. The crystal structure features inversion-related dimers linked by pairs of N—H⋯O hydrogen bonds. There are also weak C—H⋯O hydrogen bonds between these dimers.

Related literature

For the preparation of the title compound, see: Savitha & Gowda (2006 ▶). For hydrogen-bonding modes of sulfonamides, see: Adsmond & Grant (2001 ▶). For our studies on the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Gowda et al. (2003 ▶), on N-(aryl)-methanesulfonamides, see: Gowda et al. (2007 ▶) and on N-(aryl)-arylsulfonamides, see: Gelbrich et al. (2007 ▶); Perlovich et al. (2006 ▶); Gowda & Kumar (2003 ▶); Rodrigues et al. (2011 ▶).

Experimental

Crystal data

C₁₄H₁₃Cl₂NO₂S
M _r = 330.21
Monoclinic,
a = 23.067 (2) Å
b = 8.0794 (5) Å
c = 16.470 (1) Å
β = 101.575 (7)°
V = 3007.0 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 293 K
0.50 × 0.46 × 0.42 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD Detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.764, T _max = 0.796
10045 measured reflections
3067 independent reflections
2555 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.124
S = 1.09
3067 reflections
186 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.73 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 datablock(s) I, global. DOI: 10.1107/S1600536811040189/bq2307sup1.cif

e-67-o2842-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040189/bq2307Isup2.hkl

e-67-o2842-Isup2.hkl^{(150.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811040189/bq2307Isup3.cml

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)	2.11 (2)	2.948 (2)	176 (2)
C3—H3⋯O2ⁱⁱ	0.93	2.40	3.264 (2)	154 (1)

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

VZR thanks the University Grants Commission, Government of India, New Delhi, for the award of an RFSMS fellowship.

supplementary crystallographic information

Comment

The sulfonamide moiety is present in several biologically important compounds. The hydrogen bonding preferences of sulfonamides have also been investigated (Adsmond & Grant, 2001). As part of our studies on the substituent effects on the structures and other aspects of N-(aryl)-amides (Gowda et al., 2003), N-(aryl)-methanesulfonamides (Gowda et al., 2007) and N-(aryl)-arylsulfonamides (Gowda & Kumar, 2003; Rodrigues et al., 2011), in the present work, the crystal structure of 2,4-dichloro-N-(3,5-dimethylphenyl)- benzenesulfonamide (I) has been determined (Fig. 1).

In (I), the N—H bond in the C—SO₂—NH—C segment is syn to one of the meta-methyl groups in the aniline benzene ring and anti to the other. Further, the conformations of the N—C bonds in the C—SO₂—NH—C segment have gauche torsions with respect to the S═O bonds.

The molecule is bent at the S atom with C—SO₂—NH—C torsion angle of 54.94 (20)°, compared to the value of -60.84 (18)° in 2,4-dichloro-N-(3,4-dimethylphenyl)-benzenesulfonamide (II) (Rodrigues et al., 2011).

The sulfonyl and the aniline benzene rings are tilted relative to each other by 66.4 (1)°, compared to the value of 82.8 (1)° in (II)

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

In the crystal structure, the pairs of intermolecular N–H···O hydrogen bonds (Table 1) link the molecules into inversion-related dimers. There is also weak C-H···O hydrogen bonds between these dimers. Part of the crystal structure is shown in Fig. 2.

Experimental

The solution of 1,3-dichlorobenzene (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-dichlorobenzenesulfonylchloride was treated with 3,5-dimethylaniline 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 solid 2,4-dichloro-N- (3,5-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 (Savitha & Gowda, 2006).

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