Ethyl 3-bromo-1-(3-chloro­pyridin-2-yl)-1H-pyrazole-5-carboxyl­ate

He, H.-B.; Liu, S.; Tan, H.-J.; Xia, M.; Zhu, H.-J.

doi:10.1107/S1600536808039329

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o95

doi:10.1107/S1600536808039329

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Ethyl 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate

Hai-Bing He,^a Shan Liu,^a Hai-Jun Tan,^a Ming Xia ^a and Hong-Jun Zhu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: zhuhj@njut.edu.cn

(Received 16 October 2008; accepted 22 November 2008; online 13 December 2008)

The title compound, C₁₁H₉BrClN₃O₂, is an intermediate in the synthesis of Rynaxypyre, a new insecticidal anthranilic diamide used as a potent and selective ryanodine receptor activator. The dihedral angle between the aromatic ring planes is 78.7 (2)°.

Related literature

For the synthetic procedure, see: Lahm et al. (2007 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₁H₉BrClN₃O₂
M_r = 330.57
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.404 (2) Å
b = 10.024 (2) Å
c = 17.072 (3) Å
V = 1267.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.45 mm⁻¹
T = 298 (2) K
0.40 × 0.30 × 0.30 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.339, T_max = 0.424 (expected range = 0.284–0.355)
2295 measured reflections
1347 independent reflections
959 reflections with I > 2σ(I)
R_int = 0.051
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.129
S = 1.00
1347 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.42 e Å⁻³
Absolute structure: Flack (1983 ), 15 Friedel pairs
Flack parameter: 0.37

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/S1600536808039329/im2086sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039329/im2086Isup2.hkl

checkCIF report

Comment top

Ethyl 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate is one of the important intermediates in the synthesis of Rynaxypyre, a new insecticidal anthranilic diamide used as a potent and selective ryanodine receptor activator (Lahm et al., 2007).

The molecular structure of (I) is shown in Fig. 1, a full list of geometric parameters is given in the supplementary material. The bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angle of the rings A (C1—C5/N1) and B(C9—C11/N2/N3) is measured to 78.7 (2)°.

No obvious intra- or inter-molecular hydrogen bonds were observed in the crystal structure (Fig. 2).

Related literature top

For the synthetic procedure, see: Lahm et al. (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound (I) was synthesized by a method reported in the literature (Lahm et al., 2007). Crystals of the title compound were obtained by dissolving ethyl 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate (3.3 g, 10.0 mmol) in acetonitrile (60 ml) and evaporating the solvent slowly at room temperature for about 20 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 50% probability level.
	Fig. 2. A packing diagram for (I).

Ethyl 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylate top

Crystal data top

C₁₁H₉BrClN₃O₂	F(000) = 656
M_r = 330.57	D_x = 1.733 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 7.404 (2) Å	θ = 9–13°
b = 10.024 (2) Å	µ = 3.45 mm⁻¹
c = 17.072 (3) Å	T = 298 K
V = 1267.0 (4) Å³	Block, colourless
Z = 4	0.40 × 0.30 × 0.30 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	959 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.051
Graphite monochromator	θ_max = 25.3°, θ_min = 2.4°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
T_min = 0.339, T_max = 0.424	l = −20→20
2295 measured reflections	3 standard reflections every 200 reflections
1347 independent reflections	intensity decay: 1%

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)] = 0.056	H-atom parameters constrained
wR(F²) = 0.129	w = 1/[σ²(F_o²) + (0.063P)² + 0.5P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
1347 reflections	Δρ_max = 0.33 e Å⁻³
163 parameters	Δρ_min = −0.42 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 155 Frieldel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.37

Crystal data top

C₁₁H₉BrClN₃O₂	V = 1267.0 (4) Å³
M_r = 330.57	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.404 (2) Å	µ = 3.45 mm⁻¹
b = 10.024 (2) Å	T = 298 K
c = 17.072 (3) Å	0.40 × 0.30 × 0.30 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	959 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.051
T_min = 0.339, T_max = 0.424	3 standard reflections every 200 reflections
2295 measured reflections	intensity decay: 1%
1347 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	H-atom parameters constrained
wR(F²) = 0.129	Δρ_max = 0.33 e Å⁻³
S = 1.01	Δρ_min = −0.42 e Å⁻³
1347 reflections	Absolute structure: Flack (1983), 155 Frieldel pairs
163 parameters	Absolute structure parameter: 0.37
0 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
Br	0.03831 (14)	0.07498 (8)	0.79256 (5)	0.0580 (3)
Cl	0.2975 (3)	0.5607 (2)	0.90139 (15)	0.0661 (6)
O1	0.0029 (10)	0.4767 (5)	1.0803 (3)	0.0645 (19)
N1	−0.2392 (8)	0.5697 (7)	0.9219 (4)	0.0481 (16)
C1	0.0862 (11)	0.6189 (7)	0.9087 (5)	0.046 (2)
C2	0.0441 (15)	0.7564 (7)	0.9030 (4)	0.056 (2)
H2A	0.1355	0.8190	0.8964	0.067*
N2	−0.0180 (10)	0.3292 (5)	0.8505 (3)	0.0457 (17)
O2	0.0190 (8)	0.2604 (4)	1.1121 (3)	0.0483 (14)
N3	−0.0260 (10)	0.3932 (5)	0.9196 (3)	0.0442 (16)
C3	−0.1273 (14)	0.7949 (8)	0.9073 (6)	0.059 (2)
H3A	−0.1564	0.8848	0.9027	0.071*
C4	−0.2629 (11)	0.7014 (8)	0.9187 (5)	0.055 (2)
H4A	−0.3801	0.7333	0.9245	0.066*
C5	−0.0628 (13)	0.5354 (6)	0.9191 (4)	0.045 (2)
C6	0.0235 (18)	0.1666 (8)	1.2393 (5)	0.074 (3)
H6A	0.0324	0.1860	1.2943	0.111*
H6B	0.1218	0.1099	1.2241	0.111*
H6C	−0.0889	0.1224	1.2289	0.111*
C7	0.0317 (13)	0.2919 (7)	1.1945 (4)	0.0476 (19)
H7A	−0.0671	0.3499	1.2097	0.057*
H7B	0.1444	0.3377	1.2052	0.057*
C8	0.0085 (12)	0.3603 (7)	1.0617 (4)	0.046 (2)
C9	0.0042 (11)	0.3108 (6)	0.9816 (4)	0.041 (2)
C10	0.0303 (12)	0.1880 (6)	0.9503 (4)	0.0413 (17)
H10A	0.0526	0.1092	0.9773	0.050*
C11	0.0173 (11)	0.2032 (6)	0.8719 (4)	0.0383 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0822 (6)	0.0377 (4)	0.0539 (4)	0.0033 (5)	0.0035 (5)	−0.0055 (4)
Cl	0.0537 (13)	0.0473 (14)	0.0974 (17)	0.0016 (12)	0.0030 (12)	0.0009 (13)
O1	0.107 (6)	0.032 (3)	0.054 (3)	−0.003 (3)	−0.006 (4)	−0.004 (2)
N1	0.047 (4)	0.028 (4)	0.070 (4)	0.004 (4)	0.019 (3)	0.005 (4)
C1	0.045 (5)	0.034 (4)	0.058 (5)	0.004 (3)	0.002 (4)	0.000 (3)
C2	0.082 (7)	0.026 (4)	0.059 (5)	0.001 (5)	0.018 (6)	0.003 (3)
N2	0.067 (5)	0.028 (3)	0.042 (3)	0.003 (3)	−0.014 (4)	0.002 (2)
O2	0.070 (4)	0.035 (3)	0.040 (2)	0.000 (3)	−0.004 (3)	−0.001 (2)
N3	0.066 (4)	0.024 (3)	0.043 (3)	−0.003 (3)	−0.001 (3)	−0.001 (2)
C3	0.071 (7)	0.030 (5)	0.077 (6)	0.009 (5)	0.004 (6)	−0.003 (4)
C4	0.034 (5)	0.052 (5)	0.079 (6)	0.001 (4)	0.002 (5)	−0.001 (5)
C5	0.073 (6)	0.025 (4)	0.036 (4)	−0.010 (4)	−0.005 (4)	0.007 (3)
C6	0.113 (9)	0.058 (5)	0.050 (5)	0.006 (6)	−0.006 (6)	0.013 (4)
C7	0.059 (5)	0.043 (4)	0.041 (4)	0.010 (4)	−0.006 (4)	−0.005 (3)
C8	0.057 (7)	0.029 (4)	0.052 (4)	−0.008 (4)	0.009 (4)	0.001 (3)
C9	0.052 (6)	0.030 (4)	0.041 (4)	−0.001 (4)	0.000 (4)	0.001 (3)
C10	0.057 (5)	0.019 (3)	0.048 (4)	0.002 (4)	−0.003 (4)	0.003 (3)
C11	0.044 (5)	0.025 (3)	0.046 (4)	−0.004 (3)	0.003 (4)	0.001 (3)

Geometric parameters (Å, º) top

Br—C11	1.874 (6)	N3—C5	1.452 (8)
Cl—C1	1.675 (8)	C3—C4	1.387 (12)
O1—C8	1.210 (7)	C3—H3A	0.9300
N1—C4	1.334 (9)	C4—H4A	0.9300
N1—C5	1.351 (11)	C6—C7	1.472 (9)
C1—C5	1.396 (11)	C6—H6A	0.9600
C1—C2	1.416 (10)	C6—H6B	0.9600
C2—C3	1.328 (12)	C6—H6C	0.9600
C2—H2A	0.9300	C7—H7A	0.9700
N2—C11	1.340 (8)	C7—H7B	0.9700
N2—N3	1.344 (7)	C8—C9	1.454 (10)
O2—C8	1.323 (8)	C9—C10	1.356 (9)
O2—C7	1.445 (7)	C10—C11	1.351 (9)
N3—C9	1.361 (8)	C10—H10A	0.9300

C4—N1—C5	112.2 (6)	H6A—C6—H6B	109.5
C5—C1—C2	114.7 (8)	C7—C6—H6C	109.5
C5—C1—Cl	122.6 (6)	H6A—C6—H6C	109.5
C2—C1—Cl	122.6 (7)	H6B—C6—H6C	109.5
C3—C2—C1	119.3 (9)	O2—C7—C6	108.5 (6)
C3—C2—H2A	120.4	O2—C7—H7A	110.0
C1—C2—H2A	120.4	C6—C7—H7A	110.0
C11—N2—N3	102.7 (5)	O2—C7—H7B	110.0
C8—O2—C7	118.2 (5)	C6—C7—H7B	110.0
N2—N3—C9	112.7 (5)	H7A—C7—H7B	108.4
N2—N3—C5	118.2 (5)	O1—C8—O2	124.1 (7)
C9—N3—C5	129.1 (5)	O1—C8—C9	125.1 (7)
C2—C3—C4	120.2 (8)	O2—C8—C9	110.8 (6)
C2—C3—H3A	119.9	C10—C9—N3	105.5 (6)
C4—C3—H3A	119.9	C10—C9—C8	132.6 (6)
N1—C4—C3	125.4 (8)	N3—C9—C8	121.9 (6)
N1—C4—H4A	117.3	C11—C10—C9	106.1 (6)
C3—C4—H4A	117.3	C11—C10—H10A	126.9
N1—C5—C1	128.0 (6)	C9—C10—H10A	126.9
N1—C5—N3	115.5 (7)	N2—C11—C10	113.0 (6)
C1—C5—N3	116.2 (8)	N2—C11—Br	117.8 (5)
C7—C6—H6A	109.5	C10—C11—Br	129.2 (5)
C7—C6—H6B	109.5

C5—C1—C2—C3	−0.4 (12)	C8—O2—C7—C6	174.4 (8)
Cl—C1—C2—C3	178.2 (8)	C7—O2—C8—O1	−2.5 (13)
C11—N2—N3—C9	0.4 (9)	C7—O2—C8—C9	177.6 (7)
C11—N2—N3—C5	180.0 (7)	N2—N3—C9—C10	−0.9 (10)
C1—C2—C3—C4	1.2 (15)	C5—N3—C9—C10	179.6 (8)
C5—N1—C4—C3	4.9 (12)	N2—N3—C9—C8	177.7 (7)
C2—C3—C4—N1	−3.8 (16)	C5—N3—C9—C8	−1.8 (14)
C4—N1—C5—C1	−4.2 (11)	O1—C8—C9—C10	171.0 (10)
C4—N1—C5—N3	−177.9 (6)	O2—C8—C9—C10	−9.1 (13)
C2—C1—C5—N1	2.1 (12)	O1—C8—C9—N3	−7.1 (14)
Cl—C1—C5—N1	−176.5 (6)	O2—C8—C9—N3	172.8 (8)
C2—C1—C5—N3	175.8 (6)	N3—C9—C10—C11	0.9 (10)
Cl—C1—C5—N3	−2.8 (10)	C8—C9—C10—C11	−177.4 (9)
N2—N3—C5—N1	89.5 (9)	N3—N2—C11—C10	0.2 (10)
C9—N3—C5—N1	−91.0 (10)	N3—N2—C11—Br	179.4 (6)
N2—N3—C5—C1	−85.1 (9)	C9—C10—C11—N2	−0.7 (10)
C9—N3—C5—C1	94.4 (10)	C9—C10—C11—Br	−179.8 (6)

Experimental details

Crystal data
Chemical formula	C₁₁H₉BrClN₃O₂
M_r	330.57
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	7.404 (2), 10.024 (2), 17.072 (3)
V (Å³)	1267.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.45
Crystal size (mm)	0.40 × 0.30 × 0.30

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.339, 0.424
No. of measured, independent and observed [I > 2σ(I)] reflections	2295, 1347, 959
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.129, 1.01
No. of reflections	1347
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.42
Absolute structure	Flack (1983), 155 Frieldel pairs
Absolute structure parameter	0.37

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
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Lahm, G. P., Stevenson, T. M., Selby, T. P., Freudenberger, J. H., Cordova, D., Flexner, L., Bellin, C. A., Dubas, C. M., Smith, B. K., Hughes, K. A., Hollingshaus, J. G., Clark, C. E. & Benner, E. A. (2007). Bioorg. Med. Chem. Lett. 17, 6274–6279. Web of Science CrossRef PubMed CAS 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
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar