4-Chloro-N-(2,4-dimethyl­phen­yl)-2-methyl­benzene­sulfonamide

Vinola Z Rodrigues; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536811036956

. 2011 Sep 17;67(Pt 10):o2648. doi: 10.1107/S1600536811036956

4-Chloro-N-(2,4-dimethylphenyl)-2-methylbenzenesulfonamide

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

PMCID: PMC3201300 PMID: 22058774

Abstract

In the title compound, C₁₅H₁₆ClNO₂S, the C—SO₂—NH—C torsion angle is 67.45 (17)°. The two aromatic rings are tilted relative to each other by 44.5 (1)°. The crystal structure features inversion-related dimers linked by pairs of N—H⋯O hydrogen bonds..

Related literature

For the preparation of the title compound, see: Savitha & Gowda (2006 ▶). For hydrogen-bonding modes of sulfonamides, see: Adsmond & Grant (2001 ▶). For studies of the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Arjunan et al. (2004 ▶); Gowda et al. (2000 ▶), on N-(aryl)-methanesulfonamides, see: Gowda et al. (2007 ▶) and on N-(aryl)-arylsulfonamides, see: Gelbrich et al. (2007 ▶); Gowda et al. (2010 ▶); Perlovich et al. (2006 ▶); Rodrigues et al. (2011 ▶).

Experimental

Crystal data

C₁₅H₁₆ClNO₂S
M _r = 309.80
Monoclinic,
a = 8.2578 (7) Å
b = 12.665 (1) Å
c = 14.299 (2) Å
β = 92.187 (7)°
V = 1494.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 293 K
0.48 × 0.30 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.833, T _max = 0.925
5555 measured reflections
3041 independent reflections
2307 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.114
S = 1.06
3041 reflections
187 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.45 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/S1600536811036956/bt5641sup1.cif

e-67-o2648-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036956/bt5641Isup2.hkl

e-67-o2648-Isup2.hkl^{(149.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811036956/bt5641Isup3.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⋯O2ⁱ	0.83 (2)	2.27 (2)	3.072 (2)	162 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

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

supplementary crystallographic information

Comment

The sulfonamide moieties are the constituents of many biologically significant compounds. The hydrogen bonding preferences of sulfonamides have been investigated (Adsmond & Grant, 2001). As part of our studies on the substituent effects on the structures and other aspects of N-(aryl)-amides (Arjunan et al., 2004; Gowda et al., 2000), N-(aryl)-methanesulfonamides (Gowda et al., 2007) and N-(aryl)-arylsulfonamides (Gowda et al., 2010; Rodrigues et al., 2011), in the present work, the crystal structure of 4-Chloro-2-methyl-N-(2,4-dimethylphenyl)benzenesulfonamide (I) has been determined (Fig. 1).

In (I), the N—H bond in the C—SO₂—NH—C segment is syn with respect to the ortho-methyl group in the anilino benzene ring and orients towards the ortho-methyl group in the sulfonyl benzene ring. Further, the sulfonyl group orients itself away from the ortho- methyl groups in both the rings. The molecule is bent at the S atom with the C—SO₂—NH—C torsion angle of 67.5 (2), compared to the values of -66.8 (3)° and 70.3 (3)° in the two independent molecules of 4-Chloro-2-methyl-N-(2,3-dimethylphenyl)benzenesulfonamide (II) (Rodrigues et al., 2011), and -61.9 (4)° and 69.7 (4)° in the two molecules of 4-chloro-2-methyl-N-(phenyl)-benzenesulfonamide (III) and -76.5 (5)° and -48.3 (4)° in 4-chloro-2-methyl-N-(4-methylphenyl)-benzenesulfonamide (IV) (Gowda et al., 2010).

The sulfonyl and the aniline benzene rings are tilted relative to each other by 44.5 (1)°, compared to the values of 44.1 (1)° in molecule 1 and 39.7 (1)° in molecule 2 of (II), 86.6 (2)° and 83.0 (2)° in the two independent molecules of (III), and 76.6 (2)° in molecule 1 and 70.7 (2)° in molecule 2 of (IV).

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

In the crystal, the intermolecular N–H···O hydrogen bonds (Table 1) link the molecules into dimeric chains. Part of the crystal structure is shown in Fig. 2.

Experimental

The solution of m-chlorotoluene (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-methyl-4-chlorobenzenesulfonylchloride was treated with 2,4-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 4-chloro-2-methyl-N- (2,4-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 (Savitha & Gowda, 2006).

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