4-Bromo-2-((E)-{4-[(3,4-dimethyl­isoxazol-5-yl)sulfamo­yl]phen­yl}iminio­meth­yl)phenolate

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

doi:10.1107/S160053680800682X

. 2008 Mar 14;64(Pt 4):o720. doi: 10.1107/S160053680800682X

4-Bromo-2-((E)-{4-[(3,4-dimethylisoxazol-5-yl)sulfamoyl]phenyl}iminiomethyl)phenolate

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

PMCID: PMC2960962 PMID: 21202110

Abstract

The title compound, C₁₈H₁₆BrN₃O₄S, is a Schiff base ligand of 5-bromosalicylaldehyde and sulfisoxazole [or N-(3,4-dimethyl-5-isoxazol)sulfanilamide]. The present structure is a zwitterion and is a more precise reinterpretation of the structure which was originally reported by Hämäläinen, Lehtinen & Turpeinen [Arch. Pharm. (1986), 319, 415–420]. The two aromatic rings which make π–π interactions [centroid–centroid distance 3.7538 (18) Å] through intermolecular interactions. There is also a C—Br⋯π interaction [3.6333 (15) Å] with the heterocyclic ring. An intramolecular N—H⋯O hydrogen bond also exists. Dimers are formed due to intermolecular N—H⋯O hydrogen bonding. Intermolecular C—H⋯O hydrogen bonding links a methyl C atom and the phenolate O atom. The dimers are linked by C—H⋯N hydrogen bonds, where the C atom is from the Schiff base group and the N atom is of five-membered heterocyclic ring.

Related literature

For related literature, see: Chohan et al. (2008 ▶); Hämäläinen et al. (1986 ▶); Shad et al. (2008 ▶).

Experimental

Crystal data

C₁₈H₁₆BrN₃O₄S
M _r = 450.31
Monoclinic,
a = 15.3846 (10) Å
b = 7.2235 (5) Å
c = 16.5520 (11) Å
β = 93.201 (4)°
V = 1836.6 (2) Å³
Z = 4
Mo Kα radiation radiation
μ = 2.38 mm⁻¹
T = 296 (2) K
0.18 × 0.14 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.685, T _max = 0.793
18874 measured reflections
3955 independent reflections
2704 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.115
S = 1.00
3955 reflections
252 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.62 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/S160053680800682X/bq2069sup1.cif

e-64-0o720-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800682X/bq2069Isup2.hkl

e-64-0o720-Isup2.hkl^{(224.4KB, 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	0.80 (3)	1.91 (3)	2.577 (4)	141 (3)
N2—H2⋯O1ⁱ	0.75 (3)	2.09	2.828 (4)	171 (4)
C17—H17C⋯O1ⁱ	0.96	2.58	3.248 (5)	126
C7—H7⋯N3ⁱⁱ	0.93	2.53	3.420 (4)	161

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

Acknowledgments

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

supplementary crystallographic information

Comment

Sulfonamides are a class of compounds, which have been found to possess a wide range of medicinal properties. In continuation of synthesizing Schiff base ligands of substituted halogen salicylaldehyde and various sulfonamides (Chohan et al., 2008, Shad et al., 2008), We report the refinement of (5-Bromosalicy1idene)-N-(3,4-dimethyl-5-isoxazolyl)sulfanilamide (Hämäläinen et al., 1986).

During the refinement of 4-Chloro-2-[(E)-({4-[(3,4-dimethylisoxazol-5-yl) sulfamoyl]phenyl}iminio)methyl]phenolate (Shad et al., 2008) prepared from 5-chlorosalicylaldehyde and sulfisoxazole: [N-(3,4-dimethyl-5-isoxazol) sulfanilamide], it was observed that H-atom of hydroxy group shifts to N-atom of Schiff base moiety. To see the effect of sulfisoxazole on 5-Bromosalicylaldehyde, the title compound (I) has been prepared. The X-ray structure analysis clearly shows that again a zwitterion is formed due to the reaction of 5-Bromosalicylaldehyde and sulfisoxazole. The values of bond lengths and bond angles are similar to the chloro isomer and also similar to the reported by Hämäläinen et al., 1986. There exist π interaction at a distance of 3.6333 (15) Å C5—Br1···CgAⁱ [symmetry code i = x - 1/2, -y + 1/2, z - 1/2], where CgA is the center of gravity of the (A) five-membered heterocyclic ring containing O4. The π - π interaction also exists between the aromatic rings (B) and (C), containing C10 and C3 respectively. The distance between the centroids of neighbouring rings have value of 3.7538 (18) Å, CgB···CgCⁱⁱ [symmetry code ii = x, y - 1, z], here CgB and CgC represent the center of gravity of ring (B) and ring (C) respectively. The dihedral angles between the rings A/B, A/C, B/C have values of 43.30 (18)°, 44.30 (18)° and 5.56 (15)° respectively. The molecules form dimers through H-bonding between N2—H2···O1ⁱⁱⁱ [symmetry code iii = -x + 1, -y + 1, -z + 1]. These dimers are linked to each other by C7—H7···N3^iv [symmetry code iv = -x + 1/2, y - 1/2, -z + 3/2] and form a three-dimensional polymeric network. The intermolecular H-bond [C—H···O] between methyl C-atom and O-atom of aromatic ring with Bromom group. The detail of H-bonding is given in Table 1.

Experimental

Sulfisoxazole (0.5346 g, 2 mmol) in ethanol (20 ml) was mixed with ethanolic solution (10 ml) of 5-Bromosalicylaldehyde (0.402 g, 2 mmol). After refluxing for 3 h, the solution turned orange red. 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 10 days and obtained crystals of title compound. m.p; 481 K.