2,4-Dichloro-N-(2,5-dimethyl­phen­yl)benzene­sulfonamide

Vinola Z Rodrigues; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536811036968

. 2011 Sep 17;67(Pt 10):o2649. doi: 10.1107/S1600536811036968

2,4-Dichloro-N-(2,5-dimethylphenyl)benzenesulfonamide

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

PMCID: PMC3201254 PMID: 22064933

Abstract

The asymmetric unit of the title compound, C₁₄H₁₃Cl₂NO₂S, contains three independent moleules. The torsion angles of the C—SO2—NH—C segments in the three molecules are 67.5 (2), 83.4 (2) and −77.5 (2)°. The two aromatic rings are tilted relative to each other by 68.8 (1), 64.1 (1) and 68.5 (1)°. The crystal structure features dimers linked by pairs of N—H⋯O 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 our 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 ▶) and on N-(aryl)-arylsulfonamides, see: Gelbrich et al. (2007 ▶); Perlovich et al. (2006 ▶); Gowda et al. (2010 ▶).

Experimental

Crystal data

C₁₄H₁₃Cl₂NO₂S
M _r = 330.21
Monoclinic,
a = 24.3070 (8) Å
b = 14.8880 (6) Å
c = 12.4365 (5) Å
β = 94.929 (3)°
V = 4483.9 (3) Å³
Z = 12
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 293 K
0.42 × 0.36 × 0.36 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.795, T _max = 0.820
18567 measured reflections
9151 independent reflections
6822 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.099
S = 1.01
9151 reflections
556 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.34 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/S1600536811036968/bt5642sup1.cif

e-67-o2649-sup1.cif^{(32.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036968/bt5642Isup2.hkl

e-67-o2649-Isup2.hkl^{(447.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811036968/bt5642Isup3.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⋯O5ⁱ	0.83 (2)	2.24 (2)	3.033 (2)	160 (2)
N2—H2N⋯O4ⁱⁱ	0.82 (2)	2.16 (2)	2.956 (2)	167 (2)
N3—H3N⋯O2ⁱⁱⁱ	0.82 (2)	2.34 (2)	3.082 (2)	151 (2)

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

Acknowledgments

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

supplementary crystallographic information

Comment

The sulfonamide moiety is the constituent of many biologically important compounds. The hydrogen bonding preferences of sulfonamides have been investigated (Adsmond & Grant, 2001). As part of our studies on the substituent effects 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) and N-(aryl)-arylsulfonamides (Gowda et al., 2010), in the present work, the crystal structure of 2,4-dichloro-N- (2,5-dimethylphenyl)-benzenesulfonamide (I) has been determined (Fig. 1).

The asymmetric unit of (I) contains three independent moleules. The molecules are twisted at the S atom with the C—SO₂—NH—C torsion angles of 67.5 (2)° (molecule 1), 83.4 (2)° (molecule 2) and -77.5 (2)° (molecule 3), compared to the values of -85.1 (3)° and -47.2 (5)° in the major and minor components, respectively, of 2,4-dichloro-N-(2-methylphenyl)-benzenesulfonamide (II) (Gowda et al., 2010)

The sulfonyl and the aniline benzene rings in (I) are tilted relative to each other by 68.8 (1)° in molecule 1, 64.1 (1)° in molecule 2 and 68.5 (1)° in molecule 3, compared to the values of 74.9 (1)° and 71.0 (3)° in the two components of(II)

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

In the crystal structure, the pairs of intermolecular N–H···O hydrogen bonds (Table 1) link the molecules into dimers. Part of the crystal structure is shown in Fig. 2.

Experimental

The solution of 1,3-dichlorobenzene (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-dichlorobenzenesulfonylchloride was treated with 2,5-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-dichloro-N- (2,5-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.