Ethyl 3-bromo-1-(3-chloro-pyridin-2-yl)-1H-pyrazole-5-carboxyl-ate.

The title compound, C(11)H(9)BrClN(3)O(2), is an inter-mediate 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 = 330.57

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.129

S = 1.00

1347 reflections

163 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808039329/im2086sup1.cif

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

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

C11H9BrClN3O2	F(000) = 656
Mr = 330.57	Dx = 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

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

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(Fo2) + (0.063P)2 + 0.5P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.001
1347 reflections	Δρmax = 0.33 e Å−3
163 parameters	Δρmin = −0.42 e Å−3
0 restraints	Absolute structure: Flack (1983), 155 Frieldel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.37

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)