N-(2-Formyl­phen­yl)-4-toluene­sulfonamide: a second monoclinic polymorph

S Murugavel; N Manikandan; D Kannan; M Bakthadoss

doi:10.1107/S1600536812009403

. 2012 Mar 10;68(Pt 4):o1009–o1010. doi: 10.1107/S1600536812009403

N-(2-Formylphenyl)-4-toluenesulfonamide: a second monoclinic polymorph

S Murugavel ^a,^*, N Manikandan ^b, D Kannan ^c, M Bakthadoss ^c,^‡

PMCID: PMC3343975 PMID: 22589884

Abstract

The title compound, C₁₄H₁₃NO₃S, (I), is a second monoclinic polymorph. The original polymorph, (II), was reported by Mahía et al. [Acta Cryst. (1999), C55, 2158–2160]. Polymorph (II) crystalllized in the space group P2₁/c (Z = 4), whereas the title polymorph (I) occurs in the space group P2₁/n (Z = 4). The dihedral angle between the two aromatic rings is 75.9 (1)° in (I) compared to 81.9 (1)° for (II). In both polymorphs, two S(6) rings are generated by intramolecular N—H⋯O and C—H⋯O hydrogen bonds, resulting in similar molecular geometries. However, the two polymorphs differ concerning their crystal packing. In (I), molecules are linked into C(8) zigzag chains along the b axis by C—H⋯O hydrogen bonds, whereas in (II) molecules are linked by C—H⋯O hydrogen bonds, forming C(7) chains along the b axis. The title polymorph is further stabilized by intermolecular C—H⋯π and π–π interactions [centroid–centroid distance = 3.814 (1) Å]. These interactions are not evident in polymorph (II).

Related literature

For biological applications of sulfonamides, see: Connor (1998 ▶); Berredjem et al. (2000 ▶); Lee & Lee (2002 ▶); Xiao & Timberlake (2000 ▶). For the first monoclinic polymorph, see: Mahía et al. (1999 ▶). For a related structure, see: Zhang et al. (2010 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₄H₁₃NO₃S
M _r = 275.31
Monoclinic,
a = 11.5409 (4) Å
b = 8.1345 (2) Å
c = 14.1115 (5) Å
β = 97.294 (2)°
V = 1314.06 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.25 × 0.23 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.940, T _max = 0.956
16047 measured reflections
4254 independent reflections
2678 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.155
S = 1.02
4254 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812009403/im2360sup1.cif

e-68-o1009-sup1.cif^{(22.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812009403/im2360Isup2.hkl

e-68-o1009-Isup2.hkl^{(204.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812009403/im2360Isup3.cml

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

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

Cg1 is the centroid of the C8–C13 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	1.94	2.655 (2)	140
C2—H2⋯O2	0.93	2.48	3.059 (2)	120
C14—H14C⋯O3ⁱ	0.96	2.52	3.439 (3)	161
C5—H5⋯Cg1ⁱⁱ	0.93	2.82	3.658 (2)	150

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

Acknowledgments

The authors thank Dr Babu Vargheese, SAIF, IIT, Madras, India, for his help with the data collection.

supplementary crystallographic information

Comment

Sulfonamides are an important category of pharmaceutical compounds with a broad spectrum of biological activities such as herbicidal, anti-malarial, anti-convulsant and anti-hypertensive (Connor, 1998; Xiao & Timberlake, 2000; Berredjem et al., 2000; Lee & Lee, 2002). In this work we report the crystal structure of the title compound (Fig 1, Alternative name: 2–tosylaminobenzaldehyde), which is the second monoclinic polymorph reported.

The original polymorph (compound (II)) was previously reported by Mahía et al. (1999) and was shown to crystallize in the monoclinic space group P2₁/c, with a = 13.899 (7), b = 8.237 (4), c = 12.063 (6) Å, β = 105.899 (1)° and Z = 4. In the present work, the title compound crystallized in the space group P2₁/n with a = 11.5409 (4), b = 8.1345 (2), c = 14.1115 (5) Å, β = 97.294 (2)° and Z = 4. The dihedral angle between the two aromatic rings is 75.9 (1)° in (I) compared to 81.9 (1)° for (II). The bond distances in the molecule are normal and comparable to those in the previously published polymorph and in a closely related sulfonamide derivative (Zhang et al., 2010).

In both polymorphs, the molecular packing is stabilized by intramolecular N1—H1···O1 and C2—H2···O2 hydrogen bonds, generating two S(6) rings (Bernstein et al., 1995) (Table 1). However, the two polymorphs differ concerning their crystal packing. In compound (II) molecules are linked to form C(7) chains along the b axis by intermolecular C3—H3···O3 hydrogen bonds whereas in the title compound (I), molecules are linked by intermolecular C14—H14C···O3 hydrogen bonds to form C(8) zigzag chains along the b axis (Fig. 2). The crystal packing (Fig. 3) is further stabilized by C—H···π interactions between a formylphenyl H atom and the benzene ring (C8–C13) of a neighbouring molecule, with a C5—H5···Cg1ⁱⁱ distance of 3.658 (2) Å (Table 1; Cg1 is the centroid of the C8–C13 benzene ring, Symmetry code: ii = 1 - x, 1 - y, -z). Additional stability arises from aromatic π—π interaction between the benzene rings of neighbouring molecules, with Cg2—Cg2ⁱⁱ distance of 3.814 (1) Å (Fig. 3; Cg2 is the centroid of the C1—C6 benzene ring, Symmetry code: ii = 1 - x, 1 - y, -z). The C—H···π and π—π interactions are not evident in compound (II).

Experimental

To a stirred solution of (2-aminophenyl)methanol in chloroform, 1.5 equiv of pyridine and 1.5 equiv of 4-methylbenzene-1-sulfonyl chloride were added at room temperature over a period of 18 h. The resulting brown colored solution was quenched with aqueous HCl. After workup a pale brownish solid was obtained. The combined organic fractions were dried over Na₂SO₄ and partially concentrated under reduced pressure at 25°C. The product was precipitated with diethylether. Further, MnO₂ was added to a solution of 2-tosylaminobenzyl alcohol in dry 1,2-dichloroethane solvent under nitrogen atmosphere. The suspension was stirred at 80°C in reflux condition for 5 h and filtered through Celite. The filtrate was partially concentrated on a rotatory evaporator at 25°C and the product was precipitated with diethylether. Recystallization of the product from CH₂Cl₂ yielded pale yellow crystals of the title compound (Yield: 86%). Crystals of the original polymorph were prepared by evaporation of CHCl₃ from a solution of the title compound at room temperature (Mahía et al., 1999).