N-(4-Amino­phen­yl)-4-methylbenzene­sulfonamide

Jeveria Rehman; Ejaz; Islam Ullah Khan; William T A Harrison

doi:10.1107/S1600536811036191

. 2011 Sep 30;67(Pt 10):o2709. doi: 10.1107/S1600536811036191

N-(4-Aminophenyl)-4-methylbenzenesulfonamide

Jeveria Rehman ^a, Ejaz ^a, Islam Ullah Khan ^a,^*, William T A Harrison ^b

PMCID: PMC3201523 PMID: 22064752

Abstract

The title compound, C₁₃H₁₄N₂O₂S, crystallized with two independent molecules in the asymmetric unit. They both have V-shaped conformations: the dihedral angles between their benzene rings are identical [45.86 (13)°] and their C—S—N—C torsion angles are similar [67.9 (3) and 70.2 (3)°]. In the crystal, the molecules are linked by N—H⋯O and N—H⋯N hydrogen bonds, generating a three-dimensional network.

Related literature

For related structures and background to sulfonamides, see: Xing & Zeng (2005 ▶); Gelbrich et al. (2007 ▶); Khan et al. (2010 ▶, 2011 ▶).

Experimental

Crystal data

C₁₃H₁₄N₂O₂S
M _r = 262.32
Orthorhombic,
a = 5.0598 (3) Å
b = 14.7702 (11) Å
c = 35.026 (2) Å
V = 2617.7 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 296 K
0.41 × 0.35 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.907, T _max = 0.953
14160 measured reflections
6049 independent reflections
3138 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.122
S = 0.98
6049 reflections
345 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ▶), 2266 Friedel pairs
Flack parameter: −0.03 (8)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811036191/su2300sup1.cif

e-67-o2709-sup1.cif^{(23.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036191/su2300Isup2.hkl

e-67-o2709-Isup2.hkl^{(296.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811036191/su2300Isup3.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	0.70 (3)	2.33 (4)	2.996 (4)	161 (5)
N2—H2N⋯O4ⁱⁱ	0.88 (4)	2.18 (4)	3.052 (4)	172 (4)
N2—H3N⋯N4ⁱⁱⁱ	0.97 (4)	2.28 (4)	3.191 (5)	155 (4)
N3—H4N⋯O3ⁱ	0.79 (3)	2.17 (3)	2.957 (3)	170 (3)
N4—H5N⋯N2^iv	0.85 (4)	2.45 (4)	3.241 (5)	155 (4)
N4—H6N⋯O1^v	0.86 (4)	2.47 (4)	3.323 (5)	171 (4)

Open in a new tab

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

Acknowledgments

IUK thanks the Higher Education Commission of Pakistan for financial support under the project to strengthen the Materials Chemistry Laboratory at GCUL.

supplementary crystallographic information

Comment

As part of our ongoing structural studies of sulfonamides (Khan et al., 2011), the synthesis and structure of the title compound, (I) (Fig. 1), are now described. Related stuctures with different substituents replacing the para-amino group in (I) include 4-methyl-N-(4-nitrophenyl)benzenesulfonamide, (II), (Xing and Zeng, 2005) and 4-methyl-N-(4-methylphenyl)benzenesulfonamide, (III), (Khan et al., 2010). Also worthy of mention is the remarkable sudy of Gelbrich et al. (2007), who made a systematic structural comparison of no fewer than 133 crystal structures of 4,4'-disubstituted benzenesulfonamidobenzenes. However, no compounds with an amino substituent were incorporated into their survey.

There are two independent molecules (A containing S1 and B containing S2) in the asymmetric unit of (I), as shown in Fig. 1. They have similar V-shaped conformations and indeed the dihedral angles between their benzene rings are identical [45.86 (13)°]. Their C—S—N—C torsion angles [67.9 (3)° for A and 70.2 (3)° for B] are also similar. The bond angle sums for N1 and N3 [349.4 and 344.1°, respectively] indicate a clear tendancy towards pyramidal geometry for the nitrogen atoms. Otherwise, their bond lengths and angles are similar to those seen in (II) and (III). Values for the inter-ring dihedral angle and the C—S—N—C torsion angle are 86.1 (1) and 65.85 (13)°, respectively, in (II), and 70.53 (10) and -60.71 (18)°, respectively, in (III), indicating that (I), (II) and (III) have significantly different conformations.

In the crystal of (I), the molecules are linked by N—H···O and N—H···N hydrogen bonds (Table 1). Both the sulfonamide NH groups make intermolecular hydrogen bonds to the sulfonamide O-atom acceptors such that separate [100] C(4) chains of A and B are generated, with adjacent molecules related only by a unit-cell translation. The amine groups each form an N—H···N and an N—H···O link. The former bonds lead to distinctive [100] —N—H···N—H···N— C(2) chains of alternating A and B molecules, and serve to link the C(4) chains into a sheet. The latter bonds generate [001] chains of alternating A and B molecules and overall a three-dimensional array is generated (Fig. 2).

Because of the presence of the —NH₂ group, the hydrogen bonding patterns in (I) are not expected to show close similarities to those of the Gelbrich et al. (2007) study. There, the sulfonamide —NH— group was the only possible donor and the structure of (I) does not appear to match any of the groups of structures described by these workers.

Experimental

p-Toluene sulfonyl chloride (2 mmol, 0.3813 g) was added to p-phenylenediamine (1 mmol, 0.108 g) in distilled water (20 ml) in a round-bottom flask (100 ml). The suspension was stirred for 10 h at room temperature while keeping the pH between 8–9 with sodium carbonate solution (3%). The light brown precipitate formed was filtered, washed with distilled water and dried. Light brown needles of (I) were grown from methanol.