5-Bromo-4-(3,4-dimeth­oxy­phen­yl)thia­zol-2-amine

Hazem A Ghabbour; Tze Shyang Chia; Hoong-Kun Fun

doi:10.1107/S1600536812019320

. 2012 May 5;68(Pt 6):o1631–o1632. doi: 10.1107/S1600536812019320

5-Bromo-4-(3,4-dimethoxyphenyl)thiazol-2-amine

Hazem A Ghabbour ^a, Tze Shyang Chia ^b, Hoong-Kun Fun ^b,^*,^‡

PMCID: PMC3379236 PMID: 22719434

Abstract

In the title compound, C₁₁H₁₁BrN₂O₂S, the thiazole ring makes a dihedral angle of 53.16 (11)° with the adjacent benzene ring. The two methoxy groups are slightly twisted from the attached benzene ring with C—O—C—C torsion angles of −9.2 (3) and −5.5 (3)°. In the crystal, molecules are linked by a pair of N—H⋯N hydrogen bonds into an inversion dimer with an R ₂ ²(8) ring motif. The dimers are further connected by N—H⋯O hydrogen bonds into a tape along [-110].

Related literature

For applications of the thiazole ring system, see: Hargrave et al. (1983 ▶); Patt et al. (1992 ▶); Haviv et al. (1988 ▶); Jaen et al. (1990 ▶); Tsuji & Ishikawa (1994 ▶); Bell et al. (1995 ▶). For applications of aminothiazoles, see: Fink et al. (1999 ▶); Van Muijlwijk-Koezen et al. (2001 ▶); Metzger (1984 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the preparation, see: Das et al. (2006 ▶). For stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). graphic file with name e-68-o1631-scheme1.jpg

Experimental

Crystal data

C₁₁H₁₁BrN₂O₂S
M _r = 315.19
Triclinic,
a = 7.4873 (2) Å
b = 8.0359 (2) Å
c = 10.6428 (3) Å
α = 86.571 (2)°
β = 77.633 (2)°
γ = 85.330 (2)°
V = 622.82 (3) Å³
Z = 2
Mo Kα radiation
μ = 3.46 mm⁻¹
T = 100 K
0.45 × 0.20 × 0.09 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.305, T _max = 0.737
10861 measured reflections
2121 independent reflections
1888 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.071
S = 1.12
2121 reflections
164 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.17 e Å⁻³
Δρ_min = −0.73 e Å⁻³

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/S1600536812019320/is5132sup1.cif

e-68-o1631-sup1.cif^{(21.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019320/is5132Isup2.hkl

e-68-o1631-Isup2.hkl^{(104.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812019320/is5132Isup3.cml

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
N2—H2N2⋯O1ⁱ	0.78 (3)	2.40 (3)	2.992 (3)	134 (3)
N2—H2N2⋯O2ⁱ	0.78 (3)	2.37 (3)	3.112 (3)	161 (3)
N2—H1N2⋯N1ⁱⁱ	0.81 (3)	2.20 (3)	2.998 (3)	168 (3)

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

Acknowledgments

HAG thanks the Deanship of Scientific Research and Research Center, College of Pharmacy, King Saud University. HKF and TSC thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). TSC also thanks the Malaysian Government and USM for the award of a research fellowship.

supplementary crystallographic information

Comment

The thiazole ring system is a useful structural motif found in numerous biologically active molecules. This structure has found applications in drug development for the treatment of allergies (Hargrave et al., 1983), hypertension (Patt et al., 1992), inflammation (Haviv et al., 1988), schizophrenia (Jaen et al., 1990), bacterial (Tsuji & Ishikawa, 1994) and HIV infections (Bell et al., 1995). Aminothiazoles are known to be ligands of estrogen receptors (Fink et al., 1999) as well as a novel class of adenosine receptor antagonists (Van Muijlwijk-Koezen et al., 2001). Other analogues are used as fungicides, inhibiting in vivo growth of Xanthomonas, as an ingredient of herbicides or as schistosomicidal and anthelmintic drugs (Metzger, 1984).

In the title compound (Fig. 1), the thiazole ring (S1/N1/C7–C9) makes a dihedral angle of 53.16 (11)° with the adjacent benzene ring (C1–C6). The two methoxy groups (O1/C10 & O2/C11) are slightly twisted from the C1–C6 ring with torsion angles C10—O1—C3—C2 = -9.2 (3) and C11—O2—C4—C5 = -5.5 (3)°.

In the crystal packing (Fig. 2 & 3), the molecules are linked by intermolecular N2—H1N2···N1 hydrogen bonds into dimers with R₂²(8) ring motifs (Bernstein et al., 1995). The dimers are further connected by intermolecular N2—H2N2···O1 and N2—H2N2···O2 hydrogen bonds (Table 1) into infinite tapes along [110].

Experimental

The title compound was prepared from the reaction of 4-(3,4-dimethoxyphenyl)thiazol-2-amine (236 mg, 1 mmol) with bromine (161 mg, 1.1 mmol) in glacial acetic acid and heated at 80 °C for 1.5 h. Single crystals of the title compound suitable for X-ray structure determination were recrystallized from ethanol by the slow evaporation of the solvent at room temperature after several days (Das et al., 2006).