N-(3,5-Dichloro­phen­yl)-2,4-dimethyl­benzene­sulfonamide

P G Nirmala; B Thimme Gowda; Sabine Foro; Hartmut Fuess

doi:10.1107/S1600536810013504

. 2010 Apr 17;66(Pt 5):o1090. doi: 10.1107/S1600536810013504

N-(3,5-Dichlorophenyl)-2,4-dimethylbenzenesulfonamide

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

PMCID: PMC2979206 PMID: 21579143

Abstract

In the crystal structure of the title compound, C₁₄H₁₃Cl₂NO₂S, the conformation of 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 N atom, with an C—SO₂—NH—C torsion angle of −54.9 (3)°. The two benzene rings are tilted relative to each other by 82.3 (2)°. The molecules are linked into centrosymmetric R ₂ ²(8) motifs by N—H⋯O hydrogen bonds and C—H⋯π interactions along [100].

Related literature

For the preparation of the compound, see: Savitha & Gowda (2006 ▶). For our study of the effect of substituents on the structures of N-(aryl)arylsulfonamides, see: Gowda et al. (2008 ▶, 2009a ▶,b ▶). For related structures, see: Gelbrich et al. (2007 ▶); Perlovich et al. (2006 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₄H₁₃Cl₂NO₂S
M _r = 330.21
Monoclinic,
a = 23.085 (3) Å
b = 8.113 (2) Å
c = 16.503 (3) Å
β = 102.03 (2)°
V = 3022.9 (10) Å³
Z = 8
Cu Kα radiation
μ = 5.16 mm⁻¹
T = 299 K
0.55 × 0.45 × 0.38 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.164, T _max = 0.245
7561 measured reflections
2690 independent reflections
2340 reflections with I > 2σ(I)
R _int = 0.089
3 standard reflections every 120 min intensity decay: 1.0%

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.189
S = 1.14
2690 reflections
187 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: CAD-4-PC (Enraf–Nonius, 1996 ▶); cell refinement: CAD-4-PC; data reduction: REDU4 (Stoe & Cie, 1987 ▶); 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/S1600536810013504/bx2275sup1.cif

e-66-o1090-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013504/bx2275Isup2.hkl

e-66-o1090-Isup2.hkl^{(132.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.86 (4)	2.05 (5)	2.900 (4)	168 (4)
C10—H10⋯Cg1ⁱⁱ	0.93	2.92	3.834 (4)	168

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

supplementary crystallographic information

Comment

As part of a study of substituent effects on the structures of N-(aryl)arylsulfonamides (Gowda et al., 2008; 2009a,b), we report here the crystal structure of the title compound (I) , (Fig. 1). The conformation of the N—C bond in the C—SO₂—NH—C segment of the structure has gauche torsions with respect to the S═O bonds. The molecule is bent at the N atom with the C1—SO₂—NH—C7 torsion angle of -54.9 (3)°, compared to the values of 46.1 (3)° (glide image of molecule 1) and 47.7 (3)° (molecule 2) in the two independent molecules of 2,4-dimethyl-N-(phenyl)benzenesulfonamide (II) (Gowda et al., 2009a), -68.1 (3)° in N-(3,5-dichlorophenyl)benzenesulfonamide (III)(Gowda et al., 2008) ; 53.9 (2)° in 2,4-dimethyl-N-(3,5-dimethylphenyl)- benzenesulfonamide (IV) (Gowda et al., 2009b) and -69.7 (2)° in 2,4-dimethyl-N-(3,4-dichlorophenyl)benzenesulfonamide (V) (Gowda et al., 2009b).

The two benzene rings in (I) are tilted relative to each other by 82.3 (1)°, compared to the values of 67.5 (1)° (molecule 1) and 72.9 (1)° (molecule 2) in the two independent molecules of (II), 57.0 (1)° in (III), 82.1 (1)° in (IV) and 82.4 (1)° in (V). The other atomic 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) as representative examples.The molecules are linked into centrosymmetric R₂²(8) motifs by N—H···O hydrogen bonds and C—H···π interactions along [1 0 0] (Bernstein et al.,1995), 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 3,5-dichloroaniline 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-(3,5-dichlorophenyl)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.