4-Chloro-N-(2,3-dimethyl­phen­yl)-2-methyl­benzene­sulfonamide

Vinola Z Rodrigues; Sabine Foro; B Thimme Gowda; K Shakuntala

doi:10.1107/S1600536811037536

. 2011 Sep 17;67(Pt 10):o2674. doi: 10.1107/S1600536811037536

4-Chloro-N-(2,3-dimethylphenyl)-2-methylbenzenesulfonamide

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

PMCID: PMC3201417 PMID: 22065412

Abstract

The asymmetric unit of the title compound, C₁₅H₁₆ClNO₂S, contains two independent moleules. The conformation of the N—H bonds are anti to the ortho-methyl groups in the sulfonyl benzene rings of both the molecules, while the N—H bonds are anti to the ortho- and meta-methyl groups in the aniline ring of one of the molecules and syn in the other. Furthermore, the torsion angles of the C—SO₂—NH—C segments in the two molecules of are −66.8 (3) and 70.3 (3)°. The sulfonyl and the aniline benzene rings are oriented at angles of 44.1 (1) and 39.7 (1)° in the two molecules. In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules into 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 studies on the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Arjunan et al. (2004 ▶); Gowda et al. (2006 ▶), on N-(aryl)-methanesulfonamides, see: Gowda et al. (2007 ▶) and on N-(aryl)-arylsulfonamides, see: Gelbrich et al. (2007 ▶); Perlovich et al. (2006 ▶); Gowda et al. (2010 ▶).

Experimental

Crystal data

C₁₅H₁₆ClNO₂S
M _r = 309.80
Triclinic,
a = 8.2747 (7) Å
b = 11.0464 (9) Å
c = 17.021 (1) Å
α = 82.722 (7)°
β = 79.529 (7)°
γ = 80.267 (7)°
V = 1500.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 293 K
0.40 × 0.28 × 0.14 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.858, T _max = 0.947
10437 measured reflections
6064 independent reflections
4140 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.166
S = 1.12
6064 reflections
373 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.36 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/S1600536811037536/bq2304sup1.cif

e-67-o2674-sup1.cif^{(25.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037536/bq2304Isup2.hkl

e-67-o2674-Isup2.hkl^{(296.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811037536/bq2304Isup3.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⋯O3	0.85 (2)	2.15 (2)	2.971 (4)	162 (4)
N2—H2N⋯O2	0.85 (2)	2.12 (2)	2.954 (4)	166 (4)

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Acknowledgments

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

supplementary crystallographic information

Comment

The amide and 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 work on the substituent effects on the structures and other aspects of N-(aryl)-amides (Arjunan et al., 2004; Gowda et al., 2006), N-(aryl)-methanesulfonamides (Gowda et al., 2007) and N-(aryl)-arylsulfonamides (Gowda et al., 2010), in the present work, the crystal structure of 4-Chloro-2-methyl-N- (2,3-dimethylphenyl)benzenesulfonamide (I) has been determined (Fig. 1).

The asymmetric unit of (I) contains two independent moleules. The conformation of the N—H bonds are anti to the ortho-methyl groups in the sulfonyl benzene rings of both the molecules, while, the N—H bonds are anti to the ortho- and meta-methyl groups in the anilino benzene ring of one of the molecules and syn in the other.

The torsion angles of the C—SO₂—NH—C segments in the two molecules of (I) are -66.8 (3)° and 70.3 (3)°, compared to the values of -61.9 (4)° and 69.7 (4)° in the two independent molecules of 4-chloro-2-methyl- N-(phenyl)-benzenesulfonamide (II) and -76.5 (5)° and -48.3 (4)° in 4-chloro-2-methyl-N-(4-methylphenyl)-benzenesulfonamide (III) (Gowda et al., 2010).

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

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 as dimers (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 2,3-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 cc). The resultant solid 4-chloro-2-methyl-N- (2,3-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.