Methyl 5-bromo-6-methyl­picolinate

Wu, Y.-M.; Wu, C.-M.; Wang, Y.

doi:10.1107/S1600536808042104

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o134

doi:10.1107/S1600536808042104

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Methyl 5-bromo-6-methylpicolinate

Ya-Ming Wu,^a ^* Chun-Ming Wu ^b and Yong Wang ^c

^aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, No. 625 Geguan Road, Dachang, Nanjing 210048, People's Republic of China, ^bSynergetica-Changzhou, Ltd., Chunjiang Town, Xinbei District, Changzhou City 213033, Jiangsu Province, People's Republic of China, and ^cSchool of Pharmaceutical and Chemical Engineering, Taizhou University, Linhai 317000, People's Republic of China
^*Correspondence e-mail: adsony05@163.com

(Received 8 December 2008; accepted 10 December 2008; online 17 December 2008)

The title compound, C₈H₈BrNO₂, does not show any significant intermolecular π–π or C—H⋯π interactions in the crystal packing except for one weak Br⋯Br [3.715 (1) Å] interaction.

Related literature

The title compound is an important intermediate for the construction of novel supported PyOX ligands, see: Oila et al. (2005 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₈BrNO₂
M_r = 230.06
Monoclinic, P 2₁ /c
a = 18.518 (4) Å
b = 4.1040 (8) Å
c = 12.442 (3) Å
β = 109.52 (3)°
V = 891.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 4.57 mm⁻¹
T = 293 (2) K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.462, T_max = 0.658
1602 measured reflections
1602 independent reflections
975 reflections with I > 2σ(I)
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.066
S = 1.75
1602 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042104/lx2083sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808042104/lx2083Isup2.hkl

checkCIF report

Comment top

The title compound is one of important intermediates for construction of novel supported PyOX-ligands (Oila et al., 2005). Here we report the crystal structure of the title compound, methyl 5-bromo-6-methylpicolinate (Fig. 1).

In the title compound, the bond lengths and angles are within normal ranges (Allen et al., 1987). The crystal structure is stabilized by a weak Br···Brⁱ interaction at 3.715 (1) Å (Fig. 2; symmetry code as in Fig. 2).

Related literature top

The title compound is an important intermediates for the construction of novel supported PyOX ligands, see: Oila et al. (2005). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I) was prepared by a method reported in literature (Oila et al., 2005) with some modification. The crystals were obtained by dissolving I (0.2 g) in methanol (50 ml) and evaporating the solvent slowly at room temperature for about 3 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A drawing of the title molecular structure, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Br···Br interaction in the title compound. [Symmetry code: (i) -x+1, y+1/2, -z+1/2.]

Methyl 5-bromo-6-methylpicolinate top

Crystal data top

C₈H₈BrNO₂	F(000) = 456
M_r = 230.06	D_x = 1.715 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 18.518 (4) Å	θ = 10–14°
b = 4.1040 (8) Å	µ = 4.57 mm⁻¹
c = 12.442 (3) Å	T = 293 K
β = 109.52 (3)°	Block, colorless
V = 891.2 (4) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	975 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 25.3°, θ_min = 1.2°
ω/2θ scans	h = −22→20
Absorption correction: ψ scan (North et al., 1968)	k = 0→4
T_min = 0.462, T_max = 0.658	l = 0→14
1602 measured reflections	3 standard reflections every 200 reflections
1602 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.061	Hydrogen site location: difference Fourier map
wR(F²) = 0.066	H-atom parameters constrained
S = 1.75	w = 1/[σ²(F_o²)]
1602 reflections	(Δ/σ)_max < 0.000
110 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.61 e Å⁻³

Crystal data top

C₈H₈BrNO₂	V = 891.2 (4) Å³
M_r = 230.06	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.518 (4) Å	µ = 4.57 mm⁻¹
b = 4.1040 (8) Å	T = 293 K
c = 12.442 (3) Å	0.20 × 0.10 × 0.10 mm
β = 109.52 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	975 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.462, T_max = 0.658	3 standard reflections every 200 reflections
1602 measured reflections	intensity decay: 1%
1602 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.066	H-atom parameters constrained
S = 1.75	Δρ_max = 0.53 e Å⁻³
1602 reflections	Δρ_min = −0.61 e Å⁻³
110 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Br	0.41815 (4)	0.6507 (2)	0.25731 (6)	0.0546 (3)
O1	0.0882 (2)	−0.1451 (13)	0.2125 (3)	0.0691 (16)
O2	0.1349 (2)	−0.0435 (11)	0.3986 (4)	0.0533 (15)
N	0.2635 (3)	0.2009 (15)	0.3797 (4)	0.0450 (17)
C1	0.3893 (3)	0.4149 (17)	0.4811 (4)	0.067 (2)
H1A	0.3707	0.3787	0.5434	0.101*
H1B	0.4059	0.6370	0.4822	0.101*
H1C	0.4317	0.2717	0.4882	0.101*
C2	0.3260 (3)	0.3477 (18)	0.3698 (5)	0.0344 (16)
C3	0.3290 (3)	0.4444 (16)	0.2646 (5)	0.039 (2)
C4	0.2680 (3)	0.3789 (19)	0.1651 (5)	0.059 (2)
H4A	0.2702	0.4358	0.0939	0.071*
C5	0.2053 (3)	0.2298 (18)	0.1755 (5)	0.050 (2)
H5A	0.1632	0.1866	0.1109	0.060*
C6	0.2038 (3)	0.1425 (19)	0.2814 (5)	0.0426 (18)
C7	0.1372 (4)	−0.0335 (18)	0.2958 (6)	0.050 (2)
C8	0.0676 (3)	−0.1896 (19)	0.4127 (5)	0.070 (2)
H8A	0.0724	−0.1875	0.4920	0.104*
H8B	0.0627	−0.4104	0.3857	0.104*
H8C	0.0230	−0.0679	0.3698	0.104*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0482 (4)	0.0590 (5)	0.0589 (5)	−0.0020 (6)	0.0211 (3)	0.0028 (6)
O1	0.048 (3)	0.092 (4)	0.055 (4)	−0.011 (4)	0.001 (3)	−0.013 (4)
O2	0.043 (3)	0.070 (4)	0.046 (3)	−0.007 (3)	0.013 (2)	−0.002 (3)
N	0.029 (3)	0.065 (5)	0.033 (3)	−0.006 (4)	0.000 (3)	0.004 (4)
C1	0.056 (4)	0.087 (7)	0.043 (4)	−0.027 (5)	−0.004 (4)	0.012 (5)
C2	0.026 (4)	0.031 (4)	0.035 (4)	−0.003 (4)	−0.004 (3)	−0.004 (5)
C3	0.034 (4)	0.045 (6)	0.040 (4)	0.002 (4)	0.014 (4)	0.009 (4)
C4	0.049 (4)	0.088 (7)	0.033 (4)	0.004 (6)	0.005 (4)	0.031 (5)
C5	0.038 (4)	0.076 (7)	0.029 (4)	0.001 (4)	0.002 (3)	0.002 (4)
C6	0.025 (4)	0.060 (5)	0.042 (4)	0.004 (5)	0.011 (3)	−0.001 (5)
C7	0.037 (5)	0.060 (6)	0.043 (5)	0.004 (4)	0.000 (4)	−0.010 (5)
C8	0.051 (4)	0.079 (7)	0.089 (5)	−0.011 (5)	0.037 (4)	0.010 (6)

Geometric parameters (Å, º) top

Br—Brⁱ	3.715 (1)	C2—C3	1.387 (6)
Br—C3	1.884 (5)	C3—C4	1.396 (6)
O1—C7	1.218 (6)	C4—C5	1.356 (7)
O2—C7	1.294 (6)	C4—H4A	0.9300
O2—C8	1.446 (6)	C5—C6	1.375 (7)
N—C2	1.347 (6)	C5—H5A	0.9300
N—C6	1.368 (6)	C6—C7	1.491 (8)
C1—C2	1.510 (6)	C8—H8A	0.9600
C1—H1A	0.9600	C8—H8B	0.9600
C1—H1B	0.9600	C8—H8C	0.9600
C1—H1C	0.9600

C7—O2—C8	116.6 (5)	C3—C4—H4A	121.0
C2—N—C6	117.3 (5)	C4—C5—C6	120.0 (6)
C2—C1—H1A	109.5	C4—C5—H5A	120.0
C2—C1—H1B	109.5	C6—C5—H5A	120.0
H1A—C1—H1B	109.5	N—C6—C5	122.9 (6)
C2—C1—H1C	109.5	N—C6—C7	115.5 (6)
H1A—C1—H1C	109.5	C5—C6—C7	121.6 (6)
H1B—C1—H1C	109.5	O1—C7—O2	124.6 (7)
N—C2—C3	121.4 (5)	O1—C7—C6	119.4 (7)
N—C2—C1	115.2 (5)	O2—C7—C6	115.9 (6)
C3—C2—C1	123.3 (6)	O2—C8—H8A	109.5
C4—C3—C2	120.4 (5)	O2—C8—H8B	109.5
C4—C3—Br	120.5 (5)	H8A—C8—H8B	109.5
C2—C3—Br	119.1 (5)	O2—C8—H8C	109.5
C5—C4—C3	117.9 (6)	H8A—C8—H8C	109.5
C5—C4—H4A	121.0	H8B—C8—H8C	109.5

C6—N—C2—C3	1.8 (10)	C2—N—C6—C7	177.4 (6)
C6—N—C2—C1	178.4 (6)	C4—C5—C6—N	0.4 (11)
N—C2—C3—C4	−2.7 (11)	C4—C5—C6—C7	−177.5 (7)
C1—C2—C3—C4	−179.0 (6)	C8—O2—C7—O1	−2.1 (11)
N—C2—C3—Br	179.6 (5)	C8—O2—C7—C6	175.0 (6)
C1—C2—C3—Br	3.3 (9)	N—C6—C7—O1	−167.1 (7)
C2—C3—C4—C5	2.3 (11)	C5—C6—C7—O1	11.0 (11)
Br—C3—C4—C5	180.0 (5)	N—C6—C7—O2	15.6 (9)
C3—C4—C5—C6	−1.2 (11)	C5—C6—C7—O2	−166.3 (7)
C2—N—C6—C5	−0.6 (10)

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₈BrNO₂
M_r	230.06
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	18.518 (4), 4.1040 (8), 12.442 (3)
β (°)	109.52 (3)
V (Å³)	891.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.57
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.462, 0.658
No. of measured, independent and observed [I > 2σ(I)] reflections	1602, 1602, 975
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.066, 1.75
No. of reflections	1602
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.61

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
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Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
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