4-Chloro-2-[(E)-({4-[N-(3,4-dimethyl­isoxazol-5-yl)sulfamo­yl]phen­yl}iminio)meth­yl]phenolate

Hazoor A Shad; Zahid H Chohan; M Nawaz Tahir; Islam Ullah Khan

doi:10.1107/S1600536808005321

. 2008 Feb 27;64(Pt 3):o635. doi: 10.1107/S1600536808005321

4-Chloro-2-[(E)-({4-[N-(3,4-dimethylisoxazol-5-yl)sulfamoyl]phenyl}iminio)methyl]phenolate

Hazoor A Shad ^a, Zahid H Chohan ^a, M Nawaz Tahir ^b, Islam Ullah Khan ^c,^*

PMCID: PMC2960758 PMID: 21201966

Abstract

The title compound, C₁₈H₁₆ClN₃O₄S, is a Schiff base ligand in which the H atom of the hydroxy group has moved to the N atom of the imine group, resulting in a zwitterion. The structure is stabilized by an intramolecular (N—H⋯O) and five intermolecular (C—H⋯O, C—H⋯N and N—H⋯O) hydrogen bonds. The molecules are linked to each other by hydrogen bonds and form a three-dimensional polymeric network. In addition, the aromatic rings are also involved in π–π interactions [centroid–centroid distance between aromatic rings = 3.7525 (11) Å].

Related literature

For related literature, see: Chatterjee et al. (1982 ▶); Chohan et al. (2008 ▶); Hämäläinen et al. (1986 ▶); Nishimori et al. (2005 ▶).

Experimental

Crystal data

C₁₈H₁₆ClN₃O₄S
M _r = 405.85
Monoclinic,
a = 15.1871 (6) Å
b = 7.2555 (3) Å
c = 16.6267 (7) Å
β = 94.081 (2)°
V = 1827.45 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 296 (2) K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.886, T _max = 0.935
18429 measured reflections
4669 independent reflections
3443 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.127
S = 1.04
3443 reflections
250 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005321/pv2068sup1.cif

e-64-0o635-sup1.cif^{(20.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005321/pv2068Isup2.hkl

e-64-0o635-Isup2.hkl^{(224.1KB, hkl)}

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—H1⋯O1	0.87 (2)	1.85 (2)	2.574 (2)	140 (2)
C7—H7⋯N3ⁱ	0.93	2.54	3.429 (3)	161
C12—H12⋯O2ⁱ	0.93	2.59	3.391 (3)	145
C17—H17C⋯O3ⁱⁱ	0.96	2.57	3.516 (3)	168
C17—H17B⋯O1ⁱⁱⁱ	0.96	2.38	3.276 (3)	156
N2—H2⋯O1ⁱⁱⁱ	0.79 (2)	2.06 (2)	2.846 (2)	173 (2)

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

Acknowledgments

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, for funding the purchase of the diffractometer.

supplementary crystallographic information

Comment

Sulfonamides have been found to possess a wide range of medicinal properties such as antibacterial, antitumor, diuretic, anti-carbonic anhydrase, hypoglycaemic, anti-thyroid and protease inhibitor (Nishimori et al., 2005). In view of the versatile chemistry of various derivatives of sulfonamides, a continuous effort of synthesizing Schiff base ligands of substituted halogen salicylaldehyde and various sulfonamides (Chohan et al., 2008) is in progress. In the same context, we herein report the structure of the title compound, (I), derived from the reaction of sulfisoxazole [N-(3,4-dimethyl-5-isoxazol)sulfanilamide] and 5-chlorosalicylaldehyde. The crystal structures of sulfisoxazole (Chatterjee et al., 1982) and a bromo analog of (I) (Hämäläinen et al., 1986) have already been published; the later is isomorphous with (I).

In the solid state the H-atom bonded to hydroxy group in (I) has shifted to N-atom of the Schiff base moiety, resulting in the formation of a zwitterion (Fig. 1). The bond distance C2—O1 [1.302 (2) Å] in (I) compares well with 1.295 (10) Å reported for the corresponding distance in the bromo-analog. The bond lengths in the aromatic rings in (I) are similar to the corresonding bond lengths reported in its bromo-isomorph. The range of bond angles around S-atom [104.86 (10)°-121.02 (11)°] in (I) is also the same as reported [104.5 (4)°-121.2 (4)°] in the bromo-analog (Hämäläinen et al., 1986). The structure is stabilized by an intramolecular and five intermolecular H-bondings, the details of H-bonds are given in Table 1. The molecules linked to each other by H-bonds form a three-dimensional polymeric network (Fig. 2). In addition, π-π interactions between aromatic rings C8—C13 (ring A) and C1—C6 (ring B) are also observed with distance between the centers of gravity for the two rings CgA···CgB^iv (iv = x, y - 1, z) being Å. There also exists a π interaction between five-membered heterocyclic ring (ring C) and Cl1 with Cl1···CgC^v [v = x - 1/2, -y - 1/2, z - 1/2] distance of 3.5371 (11) Å. The dihedral angles between the rings A/B, A/C, B/C have values of 5.84 (9), 43.37 (11), and 43.29 (11)°, respectively.

Experimental

An ethanol solution (15 ml) of sulfisoxazole (0.5346 g, 2 mmol) was added to a solution of 5-chlorosalicylaldehyde (0.3131 g, 2 mmol) in ethanol (10 ml). The reaction mixture was refluxed for 3 h. The solution was cooled to room temperature, filtered and volume reduced to about one-third using rotary evaporator. It was then allowed to stand for 13 days, after which orange-red crystals were obtained (m.p. 509 K).