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Acta Cryst. (2008). E64, o995    [ doi:10.1107/S1600536808011914 ]

Methyl 4,6-dichloropyridine-3-carboxylate

Y. Ma and J. Liu

Abstract top

The title compound, C7H5Cl2NO2, crystallizes with two independent molecules in the asymmetric unit. The bond lengths and angles in both molecules are within normal ranges. In the crystal structure, weak intermolecular C-H...O hydrogen bonds link the molecules into layers parallel to the [010] plane.

Comment top

Methyl 4,6-dichloropyridine-3-carboxylate is a useful intermediate for the synthesis of different kinase inhibitors (Wallace et al., 2006; Bondinell et al., 2002). In this paper, we report the crystal structure of the title compound (I).

Compound (I) crystallizes with two independent molecules in the asymmetric unit (Fig. 1), all bond lengths and angles 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 (C1/C2/O1/O2; C8/C9/O3/O4) and pyridine rings in the two independent molecules are 10.9 (2) and 8.1 (4)°. In the crystal structure, weak intermolecular C—H···O hydrogen bonds link the molecules into layers parallel to the b axis.

Related literature top

For the biological activity of the title compound, see: Wallace et al. (2006); Bondinell et al. (2002). For a related structure, see: McArdle et al. (1982).

Experimental top

Methyl 4, 6-dichloropyridine-3-carboxylate was synthesized from Methyl 4, 6-dihydroxypyridine-3-carboxylate via chlorination with POCl3. The desired compound was obtained as a low melting yellow solid in 89% yield. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution in a hexane/dichloromethane mixture (1: 4 v/v) at room temperature over a period of one week.

Refinement top

All H atoms were placed in calculated positions, with C—H = 0.93 or 0.96 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2 times Ueq(C).

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
[Figure 1] Fig. 1. View of the title compound (I), with displacement ellipsoids drawn at the 40% probability level.
Methyl 4,6-dichloropyridine-3-carboxylate top
Crystal data top
C7H5Cl2NO2F000 = 832
Mr = 206.02Dx = 1.604 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1274 reflections
a = 8.033 (4) Åθ = 2.8–27.9º
b = 18.974 (9) ŵ = 0.72 mm−1
c = 11.240 (6) ÅT = 298 (2) K
β = 95.224 (8)ºBlock, colorless
V = 1705.9 (15) Å30.45 × 0.19 × 0.06 mm
Z = 8
Data collection top
Bruker SMART CCD area-detector
diffractometer		3012 independent reflections
Radiation source: fine-focus sealed tube2289 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.035
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −9→9
Tmin = 0.739, Tmax = 0.958k = −16→22
8532 measured reflectionsl = −12→13
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052H-atom parameters constrained
wR(F2) = 0.135  w = 1/[σ2(Fo2) + (0.0645P)2 + 0.3441P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
3012 reflectionsΔρmax = 0.25 e Å−3
217 parametersΔρmin = −0.18 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C7H5Cl2NO2V = 1705.9 (15) Å3
Mr = 206.02Z = 8
Monoclinic, P21/cMo Kα
a = 8.033 (4) ŵ = 0.72 mm−1
b = 18.974 (9) ÅT = 298 (2) K
c = 11.240 (6) Å0.45 × 0.19 × 0.06 mm
β = 95.224 (8)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3012 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		2289 reflections with I > 2σ(I)
Tmin = 0.739, Tmax = 0.958Rint = 0.035
8532 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.052217 parameters
wR(F2) = 0.135H-atom parameters constrained
S = 1.08Δρmax = 0.25 e Å−3
3012 reflectionsΔρmin = −0.18 e Å−3
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
xyzUiso*/Ueq
Cl10.31475 (11)0.33695 (5)0.64891 (7)0.0715 (3)
Cl40.81189 (12)0.14450 (4)1.15267 (7)0.0730 (3)
Cl30.49419 (14)0.01243 (5)0.78099 (8)0.0883 (4)
Cl20.16454 (16)0.07877 (5)0.49234 (11)0.1033 (4)
O40.0012 (3)0.39718 (12)0.3185 (2)0.0810 (7)
O10.6147 (3)0.33347 (11)0.9518 (2)0.0761 (7)
C30.6515 (3)0.21244 (15)0.9614 (2)0.0494 (7)
C40.5571 (4)0.20765 (17)0.8514 (3)0.0629 (8)
H4A0.52530.24970.81330.075*
O20.7987 (3)0.29383 (12)1.0946 (2)0.0859 (8)
C60.6496 (4)0.08658 (16)0.9608 (3)0.0586 (8)
H6A0.67990.04340.99550.070*
N10.5088 (4)0.14837 (15)0.7965 (2)0.0676 (7)
C100.1250 (3)0.30967 (15)0.4395 (2)0.0496 (7)
C110.0479 (4)0.25996 (16)0.3617 (3)0.0570 (8)
H11A−0.01520.27650.29400.068*
C130.2303 (4)0.21170 (16)0.5586 (3)0.0585 (8)
H13A0.29240.19300.62510.070*
O30.1841 (4)0.43167 (13)0.4631 (2)0.1010 (10)
C50.5558 (4)0.09031 (17)0.8522 (3)0.0603 (8)
C70.6965 (4)0.14869 (15)1.0159 (2)0.0504 (7)
C90.1096 (4)0.38562 (17)0.4109 (3)0.0574 (8)
C10.6574 (6)0.40446 (18)0.9884 (4)0.0940 (13)
H1B0.58890.43710.94050.141*
H1C0.77300.41310.97810.141*
H1D0.63880.41051.07100.141*
N20.0578 (3)0.19055 (14)0.3773 (2)0.0640 (7)
C140.2165 (4)0.28322 (15)0.5410 (2)0.0505 (7)
C20.6989 (4)0.28237 (16)1.0116 (3)0.0552 (7)
C8−0.0218 (5)0.46966 (19)0.2809 (3)0.0893 (12)
H8A−0.10380.47190.21330.134*
H8B0.08230.48830.25910.134*
H8C−0.05920.49690.34530.134*
C120.1485 (4)0.16916 (16)0.4737 (3)0.0612 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0777 (6)0.0746 (6)0.0578 (5)−0.0105 (4)−0.0170 (4)−0.0072 (4)
Cl40.0903 (7)0.0682 (5)0.0546 (5)0.0025 (4)−0.0261 (4)0.0098 (4)
Cl30.1127 (9)0.0703 (6)0.0774 (6)−0.0146 (5)−0.0161 (5)−0.0120 (4)
Cl20.1327 (10)0.0557 (5)0.1145 (8)0.0077 (6)−0.0265 (7)−0.0019 (5)
O40.0964 (19)0.0624 (14)0.0776 (15)−0.0033 (13)−0.0278 (14)0.0115 (12)
O10.0920 (18)0.0560 (13)0.0748 (15)0.0027 (12)−0.0222 (12)0.0056 (11)
C30.0457 (17)0.0590 (18)0.0425 (15)0.0017 (13)−0.0020 (12)0.0062 (13)
C40.072 (2)0.0584 (19)0.0548 (18)−0.0003 (16)−0.0144 (15)0.0074 (15)
O20.107 (2)0.0698 (16)0.0729 (15)−0.0033 (14)−0.0369 (14)−0.0034 (12)
C60.064 (2)0.0565 (18)0.0530 (18)0.0022 (15)−0.0044 (15)0.0079 (14)
N10.076 (2)0.0683 (18)0.0538 (15)−0.0015 (14)−0.0175 (13)0.0034 (13)
C100.0448 (17)0.0594 (18)0.0444 (15)−0.0022 (14)0.0035 (12)−0.0019 (13)
C110.059 (2)0.064 (2)0.0466 (16)−0.0005 (15)−0.0042 (14)−0.0028 (14)
C130.0565 (19)0.066 (2)0.0509 (17)0.0018 (15)−0.0056 (14)0.0038 (14)
O30.136 (3)0.0614 (16)0.0958 (19)−0.0204 (15)−0.0430 (18)0.0030 (13)
C50.064 (2)0.063 (2)0.0528 (17)−0.0050 (16)−0.0029 (15)−0.0045 (15)
C70.0465 (17)0.0616 (18)0.0418 (15)0.0028 (14)−0.0031 (12)0.0062 (13)
C90.058 (2)0.064 (2)0.0501 (17)−0.0045 (16)−0.0014 (15)0.0015 (15)
C10.133 (4)0.053 (2)0.090 (3)0.003 (2)−0.020 (2)−0.0003 (18)
N20.0729 (19)0.0568 (16)0.0602 (16)−0.0026 (13)−0.0062 (13)−0.0087 (13)
C140.0462 (17)0.0586 (18)0.0464 (16)−0.0040 (13)0.0034 (13)−0.0036 (13)
C20.061 (2)0.0597 (18)0.0445 (16)0.0022 (15)0.0002 (14)0.0054 (14)
C80.105 (3)0.068 (2)0.090 (3)0.002 (2)−0.016 (2)0.0210 (19)
C120.064 (2)0.0546 (18)0.064 (2)0.0040 (15)−0.0002 (16)−0.0012 (15)
Geometric parameters (Å, °) top
Cl1—C141.720 (3)N1—C51.306 (4)
Cl4—C71.723 (3)C10—C111.392 (4)
Cl3—C51.731 (3)C10—C141.393 (4)
Cl2—C121.731 (3)C10—C91.479 (4)
O4—C91.313 (4)C11—N21.330 (4)
O4—C81.446 (4)C11—H11A0.9300
O1—C21.329 (4)C13—C121.371 (4)
O1—C11.441 (4)C13—C141.374 (4)
C3—C71.389 (4)C13—H13A0.9300
C3—C41.393 (4)O3—C91.184 (4)
C3—C21.478 (4)C1—H1B0.9600
C4—N11.324 (4)C1—H1C0.9600
C4—H4A0.9300C1—H1D0.9600
O2—C21.194 (4)N2—C121.314 (4)
C6—C71.368 (4)C8—H8A0.9600
C6—C51.376 (4)C8—H8B0.9600
C6—H6A0.9300C8—H8C0.9600
C9—O4—C8116.6 (3)C3—C7—Cl4122.1 (2)
C2—O1—C1116.2 (3)O3—C9—O4122.6 (3)
C7—C3—C4115.7 (3)O3—C9—C10125.7 (3)
C7—C3—C2124.4 (2)O4—C9—C10111.8 (3)
C4—C3—C2119.8 (3)O1—C1—H1B109.5
N1—C4—C3125.6 (3)O1—C1—H1C109.5
N1—C4—H4A117.2H1B—C1—H1C109.5
C3—C4—H4A117.2O1—C1—H1D109.5
C7—C6—C5117.6 (3)H1B—C1—H1D109.5
C7—C6—H6A121.2H1C—C1—H1D109.5
C5—C6—H6A121.2C12—N2—C11115.9 (3)
C5—N1—C4115.7 (3)C13—C14—C10120.2 (3)
C11—C10—C14116.2 (3)C13—C14—Cl1117.2 (2)
C11—C10—C9120.0 (3)C10—C14—Cl1122.5 (2)
C14—C10—C9123.8 (3)O2—C2—O1122.5 (3)
N2—C11—C10124.8 (3)O2—C2—C3126.4 (3)
N2—C11—H11A117.6O1—C2—C3111.2 (3)
C10—C11—H11A117.6O4—C8—H8A109.5
C12—C13—C14117.0 (3)O4—C8—H8B109.5
C12—C13—H13A121.5H8A—C8—H8B109.5
C14—C13—H13A121.5O4—C8—H8C109.5
N1—C5—C6125.4 (3)H8A—C8—H8C109.5
N1—C5—Cl3116.1 (2)H8B—C8—H8C109.5
C6—C5—Cl3118.5 (2)N2—C12—C13125.9 (3)
C6—C7—C3120.0 (3)N2—C12—Cl2115.8 (2)
C6—C7—Cl4117.9 (2)C13—C12—Cl2118.2 (2)
C7—C3—C4—N1−0.2 (5)C11—C10—C9—O48.7 (4)
C2—C3—C4—N1179.1 (3)C14—C10—C9—O4−172.4 (3)
C3—C4—N1—C5−0.1 (5)C10—C11—N2—C12−0.3 (5)
C14—C10—C11—N2−0.9 (4)C12—C13—C14—C10−1.1 (4)
C9—C10—C11—N2178.0 (3)C12—C13—C14—Cl1178.5 (2)
C4—N1—C5—C6−0.1 (5)C11—C10—C14—C131.6 (4)
C4—N1—C5—Cl3−179.7 (2)C9—C10—C14—C13−177.3 (3)
C7—C6—C5—N10.6 (5)C11—C10—C14—Cl1−178.0 (2)
C7—C6—C5—Cl3−179.8 (2)C9—C10—C14—Cl13.1 (4)
C5—C6—C7—C3−0.9 (5)C1—O1—C2—O23.5 (5)
C5—C6—C7—Cl4179.3 (2)C1—O1—C2—C3−176.6 (3)
C4—C3—C7—C60.7 (4)C7—C3—C2—O211.1 (5)
C2—C3—C7—C6−178.5 (3)C4—C3—C2—O2−168.0 (3)
C4—C3—C7—Cl4−179.5 (2)C7—C3—C2—O1−168.8 (3)
C2—C3—C7—Cl41.3 (4)C4—C3—C2—O112.0 (4)
C8—O4—C9—O31.1 (5)C11—N2—C12—C130.9 (5)
C8—O4—C9—C10−178.8 (3)C11—N2—C12—Cl2−178.8 (2)
C11—C10—C9—O3−171.2 (3)C14—C13—C12—N2−0.2 (5)
C14—C10—C9—O37.7 (5)C14—C13—C12—Cl2179.5 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···O3i0.932.413.309 (4)162
C11—H11A···O2ii0.932.603.513 (4)168
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x−1, y, z−1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···O3i0.932.413.309 (4)162
C11—H11A···O2ii0.932.603.513 (4)168
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x−1, y, z−1.
Acknowledgements top

I do not need acknowledegements.

references
References top

Bondinell, W. E., Holt, D. A., Lago, M. A., Neeb, M. J. & Semones, M. A. (2002). World Wide Patent. WO 02 076 463.

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

McArdle, J. V., de Laubenfels, E., Shorter, A. L. & Ammon, H. L. (1982). Polyhedron, 1, 471–474.

Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Wallace, E., Hurley, B., Yang, H. W., Lyssikatos, J. & Blake, J. (2006). United States Patent US 7 144 907.