N-(3,5-Dimethyl­phen­yl)-2-nitro­benzene­sulfonamide

U Chaithanya; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536812036926

. 2012 Sep 1;68(Pt 10):o2823. doi: 10.1107/S1600536812036926

N-(3,5-Dimethylphenyl)-2-nitrobenzenesulfonamide

U Chaithanya ^a, Sabine Foro ^b, B Thimme Gowda ^a,^*

PMCID: PMC3470185 PMID: 23125629

Abstract

The asymmetric unit of the title compound, C₁₄H₁₄N₂O₄S, consists of two crystallographically independent molecules. The molecules are twisted at the S—N bonds with C—S—N—C torsion angles of 44.2 (3) and −49.3 (3)°. The dihedral angles between the benzene rings in the two molecules are 71.53 (7) and 72.11 (7)°. The amide H atoms exhibit bifurcated intra- and intermolecular hydrogen bonds; the intramolecular N—H⋯O(N) hydrogen bonds generate S(7) motifs. In the crystal, the independent molecules are separately connected through the intermolecular N—H⋯O(S) hydrogen bonds, generating a C(4) motif and a helical chain along the b axis for one molecule and an R ₂ ²(8) motif and an inversion dimer for the other. The crystal studied was a pseudo-merohedral twin with twin law (-100/0-10/001), the refined ratio of the twin domains being 0.7876 (12):0.2124 (12).

Related literature

For studies on the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Gowda & Weiss (1994 ▶); Shahwar et al. (2012 ▶), of N-arylsulfonamides, see: Chaithanya et al. (2012 ▶) and of N-chloroarylsulfonamides, see: Shetty & Gowda (2004 ▶). For hydrogen-bonding patterns and motifs, see: Adsmond et al. (2001 ▶),

Experimental

Crystal data

C₁₄H₁₄N₂O₄S
M _r = 306.33
Monoclinic,
a = 16.561 (1) Å
b = 8.1611 (6) Å
c = 21.476 (2) Å
β = 90.056 (7)°
V = 2902.6 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 K
0.48 × 0.40 × 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 = 0.894, T _max = 0.954
12941 measured reflections
5929 independent reflections
4004 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.123
S = 1.00
5929 reflections
390 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009 ▶); 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/S1600536812036926/is5184sup1.cif

e-68-o2823-sup1.cif^{(33.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036926/is5184Isup2.hkl

e-68-o2823-Isup2.hkl^{(290.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812036926/is5184Isup3.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	0.82 (2)	2.40 (2)	3.089 (3)	142 (3)
N1—H1N⋯O3	0.82 (2)	2.52 (3)	2.893 (4)	109 (2)
N3—H3N⋯O7	0.83 (2)	2.42 (3)	2.963 (3)	124 (3)
N3—H3N⋯O6ⁱⁱ	0.83 (2)	2.54 (2)	3.195 (3)	136 (3)

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

Acknowledgments

UC thanks Mangalore University for award of a research fellowship. BTG thanks the University Grants Commission, Government of India, New Delhi, for a special grant under the UGC–BSR one-time grant to faculty.

supplementary crystallographic information

Comment

As a part of our studies on the substituent effects on the structures and other aspects of N-(aryl)-amides (Gowda & Weiss, 1994; Shahwar et al., 2012), N-arylsulfonamides (Chaithanya et al., 2012) and N-chloroarylsulfonamides (Shetty & Gowda, 2004), in the present work, the crystal structure of N-(3,5-dimethylphenyl)-2-nitrobenzenesulfonamide has been determined.

The asymmetric unit of the title compound consists of two crystallographically independent molecules (Fig. 1). The conformation of the N—C bond in the —SO₂—NH—C segment has gauche torsions with respect to the S═O bonds, similar to that observed in N-(3-methylphenyl)-2-nitrobenzenesulfonamide (I) (Chaithanya et al., 2012). Further, the conformation of the N—H bond in the —SO₂—NH— segment is syn to the ortho-nitro group in the sulfonyl benzene ring. The molecules are twisted at the S—N bonds with C1—S1—N1—C7 and C15—S2—N3—C21 torsion angles of 44.2 (3) and -49.3 (3)°, respectively, compared to the value of 46.97 (16)° in (I). The dihedral angles between the sulfonyl and the anilino rings in the two molecules are 71.53 (7) and 72.11 (7)°, compared to the value of 73.64 (7)° in (I). In each molecule the amide H atom shows an intramolecular hydrogen bond (N1—H1N···O1 and N3—H3N···O7; Table 1) with the O atom of the ortho-nitro group in the sulfonyl benzene ring, generating an S(7) motif (Adsmond et al., 2001). In the crystal, the amide H atoms show intermolecular hydrogen bonds with the sulfonyl oxygen atoms of the other molecule; the N1—H1N···O1ⁱ hydrogen bond (symmetry code in Table 1) generates a C(4) motif and a helical chain along the b axis, while the N3—H3N···O6ⁱⁱ hydrogen bond (symmetry code in Table 1) an R²₂(8) motif and an inversion dimer. A part of the crystal structure is shown in Fig. 2.

Experimental

The title compound was prepared by treating 2-nitrobenzenesulfonylchloride with 3,5-dimethylaniline in the stoichiometric ratio and boiling the reaction mixture for 15 minutes. The reaction mixture was then cooled to room temperature and added to ice cold water (100 ml). The resultant solid, N-(3,5-dimethylphenyl)-2-nitrobenzenesulfonamide was filtered under suction and washed thoroughly with cold water and dilute HCl to remove the excess sulfonylchloride and aniline, respectively. It was then recrystallized to constant melting point from dilute ethanol. The purity of the compound was checked and characterized by its infrared spectra. Prism like brown single crystals of the title compound suitable for X-ray diffraction studies were grown in an ethanolic solution by slow evaporation of the solvent at room temperature.