N-(2,6-Dimethyl­phen­yl)-2,4-dimethyl­benzene­sulfonamide

P G Nirmala; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536811031102

. 2011 Aug 6;67(Pt 9):o2258. doi: 10.1107/S1600536811031102

N-(2,6-Dimethylphenyl)-2,4-dimethylbenzenesulfonamide

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

PMCID: PMC3200847 PMID: 22058917

Abstract

Molecules of the title compound, C₁₆H₁₉NO₂S, are bent at the S atom with a C—SO₂—NH—C torsion angle of −60.0 (2)°. The dihedral angle between the phenylsulfonyl and aniline rings is 41.7 (1)°. In the crystal, molecules are packed into centrosymmetric dimers through pairs of N—H⋯O(S) 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 on 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 ▶), on N-(aryl)-arylsulfonamides, see: Gelbrich et al. (2007 ▶); Nirmala et al. (2010 ▶); Perlovich et al. (2006 ▶), and on N-chloro-arylsulfonamides, see: Gowda et al. (2003 ▶).

Experimental

Crystal data

C₁₆H₁₉NO₂S
M _r = 289.38
Monoclinic,
a = 11.119 (2) Å
b = 8.312 (1) Å
c = 16.043 (2) Å
β = 97.27 (1)°
V = 1470.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 293 K
0.48 × 0.36 × 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 = 0.901, T _max = 0.957
5256 measured reflections
2685 independent reflections
2107 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.125
S = 1.04
2685 reflections
188 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.28 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/S1600536811031102/bt5591sup1.cif

e-67-o2258-sup1.cif^{(18.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811031102/bt5591Isup2.hkl

e-67-o2258-Isup2.hkl^{(131.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811031102/bt5591Isup3.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)	2.20 (2)	3.024 (3)	168 (2)

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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

The amide and sulfonamide moieties are the constituents of many biologically important compounds. The hydrogen bonding preferences of sulfonamides have been studied (Adsmond & Grant, 2001). As part of our work on the effects of substituents 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), N-(aryl)-arylsulfonamides (Nirmala et al., 2010) and N-chloro-arylsulfonamides (Gowda et al., 2003), in the present work, the crystal structure of 2,4-dimethyl-N-(2,6-dimethylphenyl)benzenesulfonamide (I) has been determined (Fig. 1).

The N—C bond in the C—SO₂—NH—C segment has gauche torsions with respect to the S═O bonds. The molecule is bent at the S atom with the C1—SO₂—NH—C7 torsion angle of -60.0 (2)°, compared to the values of 70.1 (2) and -66.0 (2)° in the two independent molecules of 2,4-dimethyl-N-(2,3-dimethylphenyl)benzenesulfonamide (II), 66.5 (2)° in 2,4-dimethyl-N-(2,4-dimethylphenyl)-benzenesulfonamide (III), 53.9 (2)° in 2,4-dimethyl-N-(3,5-dimethylphenyl)- benzenesulfonamide (IV) and 46.1 (3)° (molecule 1) and 47.7 (3)° (molecule 2) in the two independent molecules of 2,4-dimethyl-N-(phenyl)- benzenesulfonamide (V)(Nirmala et al., 2010).

The sulfonyl and the anilino benzene rings in (I) are tilted relative to each other by 41.7 (1)°, compared to the values of 41.5 (1) and 43.8 (1)° in the two molecules of (II), 41.0 (1)° in (III), 82.1 (1)° in (IV) and 67.5 (1)° (molecule 1) and 72.9 (1)° (molecule 2) in (V),

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

In the crystal, packing of molecules into chains through of N—H···O(S) hydrogen bonds (Table 1) is shown in Fig.2.

Experimental

The solution of m-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 2,6-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-dimethyl-N- (2,6-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).

The prism like colourless single crystals used in X-ray diffraction studies were grown in ethanolic solution by a slow evaporation at room temperature.