1-(5-Bromo-4-phenyl-1,3-thia­zol-2-yl)pyrrolidin-2-one

Hazem A Ghabbour; Adnan A Kadi; Hussein I El-Subbagh; Tze Shyang Chia; Hoong-Kun Fun

doi:10.1107/S160053681201954X

. 2012 May 16;68(Pt 6):o1738–o1739. doi: 10.1107/S160053681201954X

1-(5-Bromo-4-phenyl-1,3-thiazol-2-yl)pyrrolidin-2-one

Hazem A Ghabbour ^a, Adnan A Kadi ^a, Hussein I El-Subbagh ^b, Tze Shyang Chia ^c, Hoong-Kun Fun ^c,^*,^‡

PMCID: PMC3379326 PMID: 22719524

Abstract

The asymmetric unit of the title compound, C₁₃H₁₁BrN₂OS, consists of two crystallographically independent molecules (A and B). In each molecule, the pyrrolidine ring adopts an envelope conformation with a methylene C atom as the flap atom. In molecule A, the central thiazole ring makes a dihedral angle of 36.69 (11)° with the adjacent phenyl ring, whereas the corresponding angle is 36.85 (12)° in molecule B. The pyrrolidine ring is slightly twisted from the thiazole ring, with C—N—C—N torsion angles of 4.8 (3) and 3.0 (4)° in molecules A and B, respectively. In the crystal, C—H⋯π and π–π [centroid-to-centroid distance = 3.7539 (14) Å] interactions are observed. The crystal studied was a pseudo-merohedral twin with twin law (-100 0-10 101) and a refined component ratio of 0.7188 (5):0.2812 (5).

Related literature

For background to thiazoles, see: Bishayee et al. (1997 ▶); Chitamber & Wereley (1997 ▶); Bhaskar et al. (2008 ▶); Sharma et al. (2009 ▶); Bhattacharya et al. (2005 ▶); Spector et al. (1998 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶). For the stability of the temperature controller used for data collection, see: Cosier & Glazer (1986 ▶). graphic file with name e-68-o1738-scheme1.jpg

Experimental

Crystal data

C₁₃H₁₁BrN₂OS
M _r = 323.21
Monoclinic,
a = 7.5243 (3) Å
b = 14.1861 (6) Å
c = 12.4488 (6) Å
β = 107.508 (1)°
V = 1267.23 (10) Å³
Z = 4
Mo Kα radiation
μ = 3.40 mm⁻¹
T = 100 K
0.26 × 0.14 × 0.14 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.466, T _max = 0.646
30838 measured reflections
9338 independent reflections
8701 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.051
S = 0.99
9338 reflections
326 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.46 e Å⁻³
Absolute structure: Flack (1983 ▶), with 4219 Friedel pairs
Flack parameter: 0.017 (4)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681201954X/is5131sup1.cif

e-68-o1738-sup1.cif^{(33.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201954X/is5131Isup2.hkl

e-68-o1738-Isup2.hkl^{(456.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681201954X/is5131Isup3.cml

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

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

Cg1 is the centroid of the C1B–C6B ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12A—H12B⋯Cg1ⁱ	0.97	2.89	3.767 (3)	151

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Symmetry code: (i) Inline graphic .

Acknowledgments

HAG and AAK thank the Deanship of Scientific Research and the Research Center, College of Pharmacy, King Saud University. HKF and TSC thank Universiti Sains Malaysia (USM) for a Research University grant (No. 1001/PFIZIK/811160). TSC thanks the Malaysian government and USM for the award of a Research Fellowship.

supplementary crystallographic information

Comment

Thiazole is a five-membered ring system with two hetero atoms (S, N) placed at the 1 and 3 positions of the heterocycle. The nucleus is a building block in the structure of various natural products and biologically active compounds, like thiamine (vitamin-B), also in some antibiotics drugs like penicillin, micrococcin and many metabolic products of fungi and primitive marine animals (Bhaskar et al., 2008). Thiazole-containing drugs have widespread use in a variety of medical conditions such as fungal and bacterial infections, gastric ulcers, cancer, etc (Bishayee et al., 1997). Thiazole derivatives are involved frequently as the subject of drug design and synthesis efforts and they are reported to possess several activities like antibacterial, antifungal, anti-inflammatory (Sharma et al., 2009), analgesic, antitubercular, central nervous system (CNS) stimmulant activity as well as anti-HIV activity (Bhattacharya et al., 2005). Aminothiazole derivatives are well explored as agents of potential biological activities and some of the derivatives of thiazoles have shown inhibition towards herpes simplex virus (Spector et al., 1998).

The asymmetric unit of the title compound (Fig. 1) consists of two crystallographically independent molecules (A and B). In both molecules, the pyrrolidine ring (N2/C10–C13) adopts an envelope conformation with atom C11 as the flap atom [puckering parameters (Cremer & Pople, 1975), Q = 0.272 (3) Å and φ = 254.4 (5)° in molecule A; Q = 0.282 (3) Å and φ = 74.7 (5)° in molecule B]. In molecule A, the central thiazole ring (S1/N1/C7–C9) makes a dihedral angle of 36.69 (11)° with the adjacent benzene ring (C1–C6), whereas the corresponding angle is 36.85 (12)° in molecule B. The pyrrolidine ring is slightly twisted from the thiazole ring with C10—N2—C9—N1 torsion angles of 4.8 (3) and 3.0 (4)° in molecules A and B, respectively.

In the crystal packing, no significant intermoelcular hydrogen bondings are observed. The crystal packing is stabilized by C—H···Cg1 and π—π [Cg2—Cg3 = 3.7539 (14) Å; symmetry code = 1-X,1/2+Y,1-Z] interactions, where Cg1, Cg2 and Cg3 are the centroids of C1B–C6B, S1A/N1A/C7A–C9A and S1B/N1B/C7B–C9B rings, respectively.

Experimental

4-Chlorobutanoyl chloride (423 mg, 3 mmol) was added dropwise to a solution of 5-bromo-4-phenylthiazol-2-amine (255 mg, 1 mmol) and K₂CO₃ (414 mg, 3 mmol) in CHCl₃. The mixture was stirred for 48 h at room temperature and then ammonia and water were added to remove excess 4-chlorobutanoyl chloride and K₂CO₃. The organic solvent was removed in vacuum. The residue was taken up in dry toluene and the solution was refluxed for 10 h after addition of excess amount of piperidine. The mixture was cooled and the solvent was removed in vacuum to give solid which was then purified by chromatotron and crystallized from ethanol to give the single crystals.