Methyl 5-bromo-2-chloro­pyridine-3-carboxyl­ate

Yi Ma; Ya-Lun Liu

doi:10.1107/S1600536808013305

. 2008 May 14;64(Pt 6):o1072. doi: 10.1107/S1600536808013305

Methyl 5-bromo-2-chloropyridine-3-carboxylate

Yi Ma ^a,^*, Ya-Lun Liu ^b

PMCID: PMC2961526 PMID: 21202590

Abstract

The title compound, C₇H₅BrClNO₂, crystallizes with two independent molecules in the asymmetric unit. In the absence of classical intermolecular interactions, the crystal structure exhibits relatively short intermolecular Br⋯O distances [3.143 (9) and 3.162 (9)Å].

Related literature

For the biological activity of the title compound, see: Colarusso & Narjes (2004 ▶); Kim et al. (2006 ▶). For related crystal structures, see McArdle et al. (1982 ▶).

Experimental

Crystal data

C₇H₅BrClNO₂
M _r = 250.48
Triclinic,
a = 3.978 (2) Å
b = 8.153 (3) Å
c = 14.040 (2) Å
α = 96.89 (2)°
β = 96.20 (3)°
γ = 100.70 (2)°
V = 440.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 4.93 mm⁻¹
T = 298 (2) K
0.16 × 0.14 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.506, T _max = 0.638
2186 measured reflections
1818 independent reflections
1564 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.130
S = 1.09
1818 reflections
217 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 1.17 e Å⁻³
Δρ_min = −0.90 e Å⁻³
Absolute structure: Flack (1983 ▶); 70 Friedel pairs
Flack parameter: 0.01 (2)

Data collection: SMART (Bruker, 2001 ▶); 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 and local programs.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013305/cv2402sup1.cif

e-64-o1072-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808013305/cv2402Isup2.hkl

e-64-o1072-Isup2.hkl^{(89.5KB, hkl)}

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

Table 1. Selected interatomic distances (Å).

Br1⋯O3ⁱ	3.143 (9)
Br2⋯O1ⁱⁱ	3.162 (9)

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

supplementary crystallographic information

Comment

The title compound, (I), is a useful intermediate for the synthesis of various bioactive compounds (Colarusso et al., 2004; Kim et al., 2006). In this paper, we report its crystal structure.

Compound (I) crystallizes with two independent molecules in the non-centrosymmetric triclinic unit cell (Fig. 1). The bond lengths and angles in the molecules are normal and in a good agreement with those reported previously (McArdle et al., 1982). The dihedral angles between the planes of the methoxycarbonyl group (C6/C7/O1/O2; C13/C23/O3/O4) and pyridine rings in the two independent molecules are 45.8 (2) and 44.0 (3)°, respectively. In the abscence of classical intermolecular interactions, the crystal packing exhibits relatively short intermolecular Br···O distances (Table 1).

Experimental

A solution of 5-bromo-2-hydroxynicotinic acid (0.138 mol) and N, N-dimethylformamide (0.138 mol) in thionyl chloride (160 mL) was refluxed for 2 h. Thionyl chloride was evaporated and the yellow residue dissolved in anhydrous dichloromethane (200 mL), then anhydrous methanol was added dropwise. The resulting mixture was refluxed for 1 h and evaporated to afford slightly yellow oil which crystallized upon standing at room temperature. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of an ethanol solution at room temperature over a period of one week.