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

Ma, Y.; Liu, Y.-L.

doi:10.1107/S1600536808013305

organic compounds

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Volume 64| Part 6| June 2008| Page o1072

doi:10.1107/S1600536808013305

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

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

^aSchool of Chemical Engineering, Shandong Institute of Light Industry, Jinan 250353, People's Republic of China, and ^bJinan China Cotton Industry Co. Ltd, Jinan 250100, People's Republic of China
^*Correspondence e-mail: yima_2008@yahoo.cn

(Received 18 April 2008; accepted 6 May 2008; online 14 May 2008)

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, P 1
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[F² > 2σ(F²)] = 0.044
wR(F²) = 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)

Table 1
Selected interatomic distances (Å)

Br1⋯O3ⁱ	3.143 (9)
Br2⋯O1ⁱⁱ	3.162 (9)
Symmetry codes: (i) x-1, y-1, z+1; (ii) x-1, y, z-1.

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.

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top

Fig. 1. Two independent molecules of (I) with atomic numbering and displacement ellipsoids drawn at the 40% probability level.

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

Crystal data top

C₇H₅BrClNO₂	Z = 2
M_r = 250.48	F(000) = 244
Triclinic, P1	D_x = 1.890 Mg m⁻³
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.978 (2) Å	Cell parameters from 947 reflections
b = 8.153 (3) Å	θ = 2.6–24.3°
c = 14.040 (2) Å	µ = 4.93 mm⁻¹
α = 96.89 (2)°	T = 298 K
β = 96.20 (3)°	Block, colourless
γ = 100.70 (2)°	0.16 × 0.14 × 0.10 mm
V = 440.2 (3) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1818 independent reflections
Radiation source: fine-focus sealed tube	1564 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −4→3
T_min = 0.506, T_max = 0.639	k = −9→9
2186 measured reflections	l = −14→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.130	w = 1/[σ²(F_o²) + (0.0806P)²] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1818 reflections	Δρ_max = 1.17 e Å⁻³
217 parameters	Δρ_min = −0.90 e Å⁻³
3 restraints	Absolute structure: Flack (1983); 70 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (2)

Crystal data top

C₇H₅BrClNO₂	γ = 100.70 (2)°
M_r = 250.48	V = 440.2 (3) Å³
Triclinic, P1	Z = 2
a = 3.978 (2) Å	Mo Kα radiation
b = 8.153 (3) Å	µ = 4.93 mm⁻¹
c = 14.040 (2) Å	T = 298 K
α = 96.89 (2)°	0.16 × 0.14 × 0.10 mm
β = 96.20 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1818 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1564 reflections with I > 2σ(I)
T_min = 0.506, T_max = 0.639	R_int = 0.017
2186 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.130	Δρ_max = 1.17 e Å⁻³
S = 1.09	Δρ_min = −0.90 e Å⁻³
1818 reflections	Absolute structure: Flack (1983); 70 Friedel pairs
217 parameters	Absolute structure parameter: 0.01 (2)
3 restraints

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.3498 (2)	0.81123 (11)	0.74398 (8)	0.0523 (3)
Br2	0.3533 (3)	1.31291 (12)	−0.24715 (8)	0.0530 (3)
Cl1	0.8539 (9)	0.7931 (4)	0.3331 (2)	0.0552 (7)
Cl2	1.2578 (8)	1.5050 (4)	0.1624 (2)	0.0555 (7)
O1	1.083 (3)	1.2390 (10)	0.5287 (6)	0.074 (3)
O2	0.762 (2)	1.1535 (9)	0.3865 (5)	0.0522 (19)
O3	1.295 (3)	1.8504 (10)	−0.0331 (6)	0.080 (3)
O4	1.116 (2)	1.8360 (9)	0.1109 (5)	0.0529 (19)
N1	0.579 (3)	0.6646 (10)	0.4701 (7)	0.050 (2)
N2	0.843 (3)	1.3036 (11)	0.0259 (7)	0.053 (2)
C1	0.703 (3)	0.8099 (12)	0.4449 (7)	0.040 (2)
C2	0.735 (3)	0.9674 (12)	0.5010 (7)	0.037 (2)
C3	0.627 (3)	0.9656 (12)	0.5894 (7)	0.038 (2)
H3A	0.6454	1.0663	0.6303	0.045*
C4	0.490 (3)	0.8134 (12)	0.6187 (7)	0.042 (2)
C5	0.464 (3)	0.6665 (14)	0.5574 (8)	0.055 (3)
H5A	0.3658	0.5650	0.5764	0.066*
C6	0.880 (3)	1.1312 (12)	0.4727 (7)	0.043 (2)
C7	0.885 (3)	1.3097 (13)	0.3515 (8)	0.050 (3)
H7A	0.7729	1.3062	0.2869	0.076*
H7B	1.1297	1.3255	0.3511	0.076*
H7C	0.8330	1.4015	0.3931	0.076*
C8	0.995 (3)	1.4644 (13)	0.0517 (8)	0.042 (2)
C9	0.973 (3)	1.5908 (12)	−0.0031 (7)	0.039 (2)
C10	0.783 (3)	1.5431 (12)	−0.0957 (7)	0.042 (2)
H10A	0.7706	1.6217	−0.1381	0.050*
C11	0.616 (3)	1.3777 (12)	−0.1223 (7)	0.040 (2)
C12	0.647 (3)	1.2631 (13)	−0.0611 (8)	0.049 (3)
H12A	0.5287	1.1523	−0.0800	0.059*
C13	1.144 (3)	1.7723 (13)	0.0234 (7)	0.042 (2)
C14	1.289 (3)	2.0069 (11)	0.1478 (8)	0.047 (3)
H14A	1.2448	2.0350	0.2130	0.071*
H14B	1.2055	2.0824	0.1079	0.071*
H14C	1.5334	2.0172	0.1470	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0550 (6)	0.0621 (6)	0.0479 (7)	0.0190 (5)	0.0166 (5)	0.0206 (5)
Br2	0.0487 (6)	0.0544 (6)	0.0496 (7)	0.0118 (4)	−0.0056 (5)	−0.0094 (5)
Cl1	0.068 (2)	0.0575 (15)	0.0389 (14)	0.0144 (14)	0.0110 (12)	−0.0028 (12)
Cl2	0.067 (2)	0.0589 (16)	0.0397 (14)	0.0138 (14)	−0.0012 (12)	0.0113 (12)
O1	0.092 (7)	0.049 (4)	0.064 (5)	−0.012 (5)	−0.013 (5)	0.010 (4)
O2	0.058 (5)	0.050 (4)	0.047 (4)	0.005 (4)	0.004 (4)	0.013 (3)
O3	0.115 (8)	0.056 (5)	0.059 (5)	−0.019 (5)	0.029 (5)	0.005 (4)
O4	0.073 (6)	0.041 (4)	0.042 (4)	0.005 (4)	0.014 (4)	−0.001 (3)
N1	0.059 (7)	0.034 (5)	0.053 (6)	0.009 (4)	−0.006 (5)	−0.001 (4)
N2	0.066 (7)	0.044 (5)	0.048 (6)	0.007 (5)	0.012 (5)	0.011 (4)
C1	0.035 (6)	0.041 (6)	0.043 (6)	0.006 (4)	0.007 (5)	0.003 (5)
C2	0.033 (6)	0.037 (5)	0.040 (5)	0.005 (4)	−0.002 (4)	0.006 (4)
C3	0.042 (6)	0.041 (5)	0.031 (5)	0.011 (4)	0.007 (4)	0.006 (4)
C4	0.039 (6)	0.045 (6)	0.043 (6)	0.013 (4)	0.002 (4)	0.004 (4)
C5	0.057 (8)	0.047 (6)	0.057 (7)	0.005 (5)	−0.001 (5)	0.010 (5)
C6	0.043 (7)	0.044 (6)	0.035 (5)	0.005 (5)	−0.001 (4)	−0.001 (4)
C7	0.070 (8)	0.037 (6)	0.049 (7)	0.005 (5)	0.024 (6)	0.019 (5)
C8	0.049 (7)	0.039 (6)	0.041 (6)	0.015 (5)	0.015 (5)	0.002 (4)
C9	0.047 (6)	0.038 (5)	0.033 (5)	0.006 (5)	0.013 (4)	0.006 (4)
C10	0.051 (7)	0.039 (5)	0.037 (5)	0.011 (5)	0.012 (4)	0.005 (4)
C11	0.031 (6)	0.045 (6)	0.044 (6)	0.004 (4)	0.004 (4)	0.005 (4)
C12	0.049 (7)	0.042 (6)	0.052 (6)	0.003 (5)	0.009 (5)	−0.001 (5)
C13	0.038 (6)	0.049 (6)	0.039 (6)	0.007 (5)	0.006 (4)	0.011 (4)
C14	0.060 (7)	0.024 (5)	0.051 (7)	0.003 (5)	0.000 (5)	−0.004 (4)

Geometric parameters (Å, º) top

Br1—C4	1.902 (11)	C3—C4	1.389 (14)
Br2—C11	1.902 (10)	C3—H3A	0.9300
Cl1—C1	1.740 (10)	C4—C5	1.370 (15)
Cl2—C8	1.736 (12)	C5—H5A	0.9300
O1—C6	1.215 (11)	C7—H7A	0.9600
O2—C6	1.296 (11)	C7—H7B	0.9600
O2—C7	1.439 (12)	C7—H7C	0.9600
O3—C13	1.215 (11)	C8—C9	1.368 (14)
O4—C13	1.299 (13)	C9—C10	1.403 (13)
O4—C14	1.441 (12)	C9—C13	1.494 (14)
N1—C1	1.302 (12)	C10—C11	1.376 (13)
N1—C5	1.351 (15)	C10—H10A	0.9300
N2—C8	1.327 (13)	C11—C12	1.357 (13)
N2—C12	1.346 (14)	C12—H12A	0.9300
C1—C2	1.400 (13)	C14—H14A	0.9600
C2—C3	1.357 (13)	C14—H14B	0.9600
C2—C6	1.471 (13)	C14—H14C	0.9600

Br1···O3ⁱ	3.143 (9)	Br2···O1ⁱⁱ	3.162 (9)

C6—O2—C7	119.8 (8)	H7A—C7—H7C	109.5
C13—O4—C14	119.5 (9)	H7B—C7—H7C	109.5
C1—N1—C5	117.0 (9)	N2—C8—C9	125.6 (11)
C8—N2—C12	116.7 (9)	N2—C8—Cl2	114.0 (8)
N1—C1—C2	125.8 (9)	C9—C8—Cl2	120.4 (8)
N1—C1—Cl1	113.3 (8)	C8—C9—C10	116.4 (9)
C2—C1—Cl1	120.9 (7)	C8—C9—C13	126.8 (9)
C3—C2—C1	116.1 (8)	C10—C9—C13	116.7 (8)
C3—C2—C6	118.3 (9)	C11—C10—C9	118.6 (8)
C1—C2—C6	125.6 (9)	C11—C10—H10A	120.7
C2—C3—C4	120.0 (9)	C9—C10—H10A	120.7
C2—C3—H3A	120.0	C12—C11—C10	120.1 (9)
C4—C3—H3A	120.0	C12—C11—Br2	121.1 (7)
C5—C4—C3	119.2 (10)	C10—C11—Br2	118.8 (7)
C5—C4—Br1	121.0 (8)	N2—C12—C11	122.5 (9)
C3—C4—Br1	119.8 (7)	N2—C12—H12A	118.8
N1—C5—C4	122.0 (10)	C11—C12—H12A	118.8
N1—C5—H5A	119.0	O3—C13—O4	124.2 (9)
C4—C5—H5A	119.0	O3—C13—C9	121.9 (9)
O1—C6—O2	123.3 (9)	O4—C13—C9	114.0 (8)
O1—C6—C2	121.6 (9)	O4—C14—H14A	109.5
O2—C6—C2	115.0 (8)	O4—C14—H14B	109.5
O2—C7—H7A	109.5	H14A—C14—H14B	109.5
O2—C7—H7B	109.5	O4—C14—H14C	109.5
H7A—C7—H7B	109.5	H14A—C14—H14C	109.5
O2—C7—H7C	109.5	H14B—C14—H14C	109.5

C5—N1—C1—C2	1.3 (16)	C12—N2—C8—C9	−0.8 (17)
C5—N1—C1—Cl1	178.3 (8)	C12—N2—C8—Cl2	−177.4 (8)
N1—C1—C2—C3	0.5 (16)	N2—C8—C9—C10	−2.7 (16)
Cl1—C1—C2—C3	−176.3 (7)	Cl2—C8—C9—C10	173.7 (8)
N1—C1—C2—C6	179.1 (9)	N2—C8—C9—C13	−179.3 (11)
Cl1—C1—C2—C6	2.4 (15)	Cl2—C8—C9—C13	−3.0 (15)
C1—C2—C3—C4	−1.0 (14)	C8—C9—C10—C11	4.3 (14)
C6—C2—C3—C4	−179.8 (10)	C13—C9—C10—C11	−178.7 (9)
C2—C3—C4—C5	−0.1 (15)	C9—C10—C11—C12	−2.6 (15)
C2—C3—C4—Br1	178.4 (8)	C9—C10—C11—Br2	179.2 (8)
C1—N1—C5—C4	−2.5 (16)	C8—N2—C12—C11	2.8 (16)
C3—C4—C5—N1	2.0 (16)	C10—C11—C12—N2	−1.1 (16)
Br1—C4—C5—N1	−176.5 (8)	Br2—C11—C12—N2	177.1 (9)
C7—O2—C6—O1	2.9 (18)	C14—O4—C13—O3	−3.9 (17)
C7—O2—C6—C2	179.6 (10)	C14—O4—C13—C9	175.8 (10)
C3—C2—C6—O1	43.6 (16)	C8—C9—C13—O3	133.7 (12)
C1—C2—C6—O1	−135.1 (12)	C10—C9—C13—O3	−42.9 (15)
C3—C2—C6—O2	−133.2 (10)	C8—C9—C13—O4	−46.0 (15)
C1—C2—C6—O2	48.2 (15)	C10—C9—C13—O4	137.4 (10)

Symmetry codes: (i) x−1, y−1, z+1; (ii) x−1, y, z−1.

Experimental details

Crystal data
Chemical formula	C₇H₅BrClNO₂
M_r	250.48
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	3.978 (2), 8.153 (3), 14.040 (2)
α, β, γ (°)	96.89 (2), 96.20 (3), 100.70 (2)
V (Å³)	440.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.93
Crystal size (mm)	0.16 × 0.14 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.506, 0.639
No. of measured, independent and observed [I > 2σ(I)] reflections	2186, 1818, 1564
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.130, 1.09
No. of reflections	1818
No. of parameters	217
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.17, −0.90
Absolute structure	Flack (1983); 70 Friedel pairs
Absolute structure parameter	0.01 (2)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008) and local programs.

Selected interatomic distances (Å) top

Br1···O3ⁱ

3.143 (9)

Br2···O1ⁱⁱ

3.162 (9)

Symmetry codes: (i) x−1, y−1, z+1; (ii) x−1, y, z−1.

References

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Colarusso, S. & Narjes, F. (2004). World Patent WO 04 110 442. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Kim, Y., Close, J., Duggan, M. E., Hanney, B., Meissner, R. S., Musselman, J., Perkins, J. J. & Wang, J. B. (2006). World Patent WO 06 060 108. Google Scholar
McArdle, J. V., de Laubenfels, E., Shorter, A. L. & Ammon, H. L. (1982). Polyhedron, 1, 471–474. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 64| Part 6| June 2008| Page o1072

doi:10.1107/S1600536808013305

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