2-Bromo-4-phenyl-1,3-thia­zole

Alexander S Bunev; Yana I Rudakova; Vladimir E Statsyuk; Gennady I Ostapenko; Victor N Khrustalev

doi:10.1107/S160053681400066X

. 2014 Jan 15;70(Pt 2):o139. doi: 10.1107/S160053681400066X

2-Bromo-4-phenyl-1,3-thiazole

Alexander S Bunev ^a,^*, Yana I Rudakova ^a, Vladimir E Statsyuk ^a, Gennady I Ostapenko ^a, Victor N Khrustalev ^b

PMCID: PMC3998304 PMID: 24764865

Abstract

In the title molecule, C₉H₆BrNS, the planes of the 2-bromo-1,3-thiazole and phenyl rings are inclined at 7.45 (10)° with respect to each other. In the crystal, molecules related by a centre of symmetry are held together via π–π interactions, with a short distance of 3.815 (2) Å between the centroids of the five- and six-membered rings. The crystal packing exhibits short intermolecular S⋯Br contacts of 3.5402 (6) Å.

Related literature

For syntheses and properties of compounds containing a thiazole fragment, see: Kelly & Lang (1995 ▶); Nicolaou et al. (1999 ▶); Cosford et al. (2003 ▶); Fyfe et al. (2004 ▶); Hamill et al. (2005 ▶). For the crystal structures of related compounds, see: Abbenante et al. (1996 ▶); Zhao et al. (2011 ▶); Ghabbour, Chia et al. (2012 ▶); Ghabbour, Kadi et al. (2012 ▶). graphic file with name e-70-0o139-scheme1.jpg

Experimental

Crystal data

C₉H₆BrNS
M _r = 240.12
Monoclinic,
a = 5.8934 (3) Å
b = 10.6591 (6) Å
c = 13.8697 (7) Å
β = 90.812 (1)°
V = 871.18 (8) Å³
Z = 4
Mo Kα radiation
μ = 4.89 mm⁻¹
T = 120 K
0.15 × 0.12 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.527, T _max = 0.591
12144 measured reflections
2780 independent reflections
2258 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.068
S = 1.03
2780 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681400066X/cv5440sup1.cif

e-70-0o139-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681400066X/cv5440Isup2.hkl

e-70-0o139-Isup2.hkl^{(136.5KB, hkl)}

Click here for additional data file.^{(3.1KB, cml)}

Supporting information file. DOI: 10.1107/S160053681400066X/cv5440Isup3.cml

CCDC reference: http://scripts.iucr.org/cgi-bin/cr.cgi?rm=csd&csdid=980985

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors are grateful to the Ministry of Education and Science of the Russian Federation (State program No. 3.1168.2011).

supplementary crystallographic information

1. Comment

1,3–Thiazole rings appear in many compounds that exhibit important biological and pharmacological activities. For example, these rings feature in all the potent epothilones (Nicolaou et al., 1999) used aganist multidrug–resistant tumor cell lines. They are also found among pharmaceuticals used for the treatment of type 2 diabetes (Fyfe et al., 2004), antibiotic-like compounds (Kelly et al., 1995), and metabotropic glutamate receptor subtype (mGluR5) antagonists (Cosford et al., 2003; Hamill et al., 2005). Herewith we present the title compound (I) prepared by the reaction of 2–amino–4–phenylthiazole with n-butyl nintrine and CuBr (Figure 1).

In I (Fig. 2), the bond lengths and angles are in a good agreement with those found in the related compounds (Abbenante et al., 1996; Zhao et al., 2011; Ghabbour, Chia et al., 2012; Ghabbour, Kadi et al., 2012). The 2-bromo-1,3-thiazole mean plane and phenyl ring are twisted by 7.45 (10)°.

In the crystal, the molecules related by center of symmetry held together viaπ···π interactions proved by short Cg⁵···Cg⁶ⁱ distance of 3.815 (2) Å between the centroids of five-membered (Cg⁵) and six-membered (Cg⁶) rings [symmetry code: (i) –x, 1–y, 1–z]. The crystal packing exhibits short intermolecular S···Brⁱⁱ contacts of 3.5402 (6) Å (Figure 3) [symmetry code: (ii) -1 + x, y, z].

2. Experimental

The 4–phenyl–2–aminothiazole (8.1 g, 46.9 mmol) and CuBr (10.7 g, 74.6 mmol) were dissolved in acetonitrile at room temperature. n-Butyl nitrite (8.7 ml, 7.69 g, 74.6 mmol) was added with stirring, and the solution was heated to 333 K. The reaction completed after 15 min. The reaction mixture was then evaporated to dryness in vacuo. The residue was dissolved in ethyl acetate (50 ml) and washed with ammonia solution (0.1 M, 2 × 50). The organic layer was dried over MgSO₄ and evaporated to dryness in vacuo. The residue was purified by chromatography on silica gel (heptane–ethylacetate; 70:3, v/v). The residue crystallized from 5% soluition in heptane. Yield is 53%. The single-crystal of the product I was obtained by slow crystallization from hexane. M.p. = 327–328 K. IR (KBr), ν/cm^-1: 3098, 3063, 1476, 1420, 1263, 1070, 1010, 836, 730, 689. ¹H NMR (500 MHz, DMSO-d₆, 304 K): 7.40–6.37 (m, 1H, Ph), 7.46 (t, 2H, J = 7.63, Ph), 7.92 (d, 2H, J = 7.32, Ph), 8.16 (s, 1H, thiazole). Anal. Calcd for C₉H₆BrNS: C, 45.02; H, 2.52. Found: C, 45.09; H, 2.57.