2,4-Dimethyl-N-(4-methyl­phen­yl)benzene­sulfonamide

P G Nirmala; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536810049627

. 2010 Dec 4;67(Pt 1):o6. doi: 10.1107/S1600536810049627

2,4-Dimethyl-N-(4-methylphenyl)benzenesulfonamide

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

PMCID: PMC3050229 PMID: 21522770

Abstract

The asymmetric unit of the crystal of the title compound, C₁₅H₁₇NO₂S, contains two independent molecules, which are twisted at the S—N bonds with C—SO₂—NH—C torsion angles of 48.3 (2) (molecule 1) and −75.7 (3)° (molecule 2). The dihedral angles between the benzene rings are 72.0 (1) (molecule 1) and 78.3 (1)° (molecule 2). The crystal structure features inversion dimers linked by pairs of N—H⋯O hydrogen bonds.

Related literature

For the preparation of the title compound, see: Savitha & Gowda (2006 ▶). For our studies of the effect of substituents on the structures of N-(aryl)arylsulfonamides, see: Gowda et al. (2009 ▶); Nirmala et al. (2009 ▶, 2010 ▶). For related structures, see: Gelbrich et al. (2007 ▶); Perlovich et al. (2006 ▶).

Experimental

Crystal data

C₁₅H₁₇NO₂S
M _r = 275.36
Monoclinic,
a = 10.623 (1) Å
b = 10.770 (1) Å
c = 25.513 (2) Å
β = 97.927 (6)°
V = 2891.0 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 299 K
0.40 × 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 = 0.917, T _max = 0.957
10876 measured reflections
5282 independent reflections
3743 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.116
S = 1.03
5282 reflections
355 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.23 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/S1600536810049627/bq2257sup1.cif

e-67-000o6-sup1.cif^{(25.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049627/bq2257Isup2.hkl

e-67-000o6-Isup2.hkl^{(258.7KB, 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⋯O3ⁱ	0.85 (1)	2.15 (1)	2.991 (2)	169 (2)
N2—H2N⋯O2ⁱⁱ	0.85 (1)	2.03 (1)	2.877 (2)	175 (3)

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

supplementary crystallographic information

Comment

As part of a study of the effect of substitutions on the structures of N-(aryl)-arylsulfonamides (Gowda et al. , 2009; Nirmala et al., 2009; 2010), in the present work, the structure of 2,4-dimethyl-N-(4-methylphenyl)benzenesulfonamide (I) has been determined (Fig. 1). The asymmetric unit of (I) contains two independent molecules. The molecules are twisted at the S—N bonds with the C1—SO₂—NH—C7 torsion angles of -48.3 (2)° (molecule 1) and -75.7 (3)° (molecule 2), compared to the values of 71.6 (1)° in 2,4-dimethyl-N-(2-methylphenyl)benzenesulfonamide (II) (Nirmala et al., 2009), -58.4 (2)° in 2,4-dimethyl-N-(3-methylphenyl)benzenesulfonamide (III) (Nirmala et al., 2010) and -46.1 (3)° (molecule 1) & 47.7 (3)° (molecule 2) in the two molecules of 2,4-dimethyl-N-(phenyl)- benzenesulfonamide (IV)(Gowda et al., 2009).

The sulfonyl benzene and the aniline benzene rings in (I) are tilted relative to each other by 72.0 (1)° (molecule 1) and 78.3 (1)° (molecule 2), compared to the values of 47.0 (1)° in (II), 47.1 (1)° in (III), and 67.5 (1)° in molecule 1 and 72.9 (1)° in molecule 2 of (IV).

The other bond parameters in (I) are similar to those observed in (II), (III), (IV) and other aryl sulfonamides (Perlovich et al., 2006; Gelbrich et al., 2007). The crystal packing of molecules in (I) via N—H···O(S) hydrogen bonds (Table 1) is shown in Fig.2.

Experimental

The solution of 1,3-xylene (1,3-dimethylbenzene) (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 p-toluidine 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-(4-methylphenyl)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.