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Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): o115.
Published online 2009 December 12. doi:  10.1107/S1600536809052532
PMCID: PMC2980109

(4-Bromo-3,5-dimethyl-1H-pyrazol-1-yl)(2,6-difluoro­phen­yl)methanone

Abstract

There are two mol­ecules in the asymmetric unit of the title compound, C12H9BrF2N2O. They have very similar conformations: the dihedral angles between their pyrazole and benzene ring systems are 78.4 (3) and 78.6 (4)°. In the crystal, weak aromatic π–π stacking [centroid–centroid separation = 3.696 (5) Å] helps to establish the packing.

Related literature

For background to pyrazole derivatives in agrochemical and medicinal research, see: Sabbagh et al. (2009 [triangle]); Zheng et al. (2009 [triangle]).

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Object name is e-66-0o115-scheme1.jpg

Experimental

Crystal data

  • C12H9BrF2N2O
  • M r = 315.12
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o115-efi1.jpg
  • a = 7.116 (3) Å
  • b = 29.304 (10) Å
  • c = 11.674 (4) Å
  • β = 91.533 (5)°
  • V = 2433.5 (15) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 3.39 mm−1
  • T = 173 K
  • 0.17 × 0.17 × 0.17 mm

Data collection

  • Rigaku Saturn724+ CCD diffractometer
  • Absorption correction: numerical (CrystalClear; Rigaku, 2008 [triangle]) T min = 0.596, T max = 0.596
  • 15188 measured reflections
  • 4276 independent reflections
  • 3819 reflections with I > 2σ(I)
  • R int = 0.060

Refinement

  • R[F 2 > 2σ(F 2)] = 0.077
  • wR(F 2) = 0.158
  • S = 1.27
  • 4276 reflections
  • 329 parameters
  • H-atom parameters constrained
  • Δρmax = 1.08 e Å−3
  • Δρmin = −0.47 e Å−3

Data collection: CrystalClear (Rigaku, 2008 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809052532/hb5260sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809052532/hb5260Isup2.hkl

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

Acknowledgments

This work was supported by National Technology System for the Grape Industry, the Major State Basic Research Development Program of China (No. 2006CB101907 and No. 2010CB126106), and the 863 high-tech key project of China (2006AA10A203).

supplementary crystallographic information

Experimental

The title compound (0.2 g) was dissolved in ethanol (50 ml) at room temperature. Colourless crystals of compound (I) were obtained through slow evaporation after two weeks.

Refinement

The H atoms were placed at calculated positions, with C—H ═ 0.93–0.98 Å, and refined as riding with Uiso(H) = 1.2–1.5Uep(C).

Figures

Fig. 1.
The molecular structure of the title compound showing 50% probability displacement ellipsoids and atom-numbering scheme.

Crystal data

C12H9BrF2N2OF(000) = 1248
Mr = 315.12Dx = 1.720 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 768 reflections
a = 7.116 (3) Åθ = 2.2–27.5°
b = 29.304 (10) ŵ = 3.39 mm1
c = 11.674 (4) ÅT = 173 K
β = 91.533 (5)°Block, colourless
V = 2433.5 (15) Å30.17 × 0.17 × 0.17 mm
Z = 8

Data collection

Rigaku Saturn724+ CCD diffractometer4276 independent reflections
Radiation source: sealed tube3819 reflections with I > 2σ(I)
graphiteRint = 0.060
ω scans at fixed χ = 45°θmax = 25.0°, θmin = 2.8°
Absorption correction: numerical (CrystalClear; Rigaku, 2008)h = −6→8
Tmin = 0.596, Tmax = 0.596k = −34→34
15188 measured reflectionsl = −12→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.077Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158H-atom parameters constrained
S = 1.27w = 1/[σ2(Fo2) + (0.0402P)2 + 7.5951P] where P = (Fo2 + 2Fc2)/3
4276 reflections(Δ/σ)max < 0.001
329 parametersΔρmax = 1.08 e Å3
0 restraintsΔρmin = −0.47 e Å3

Special details

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)

xyzUiso*/Ueq
Br10.48772 (10)0.41014 (2)0.89703 (6)0.0409 (2)
Br21.00200 (10)0.31950 (3)1.09739 (6)0.0491 (3)
F10.7911 (6)0.30667 (16)1.4485 (4)0.0586 (12)
F20.1573 (5)0.32948 (15)1.3484 (3)0.0503 (11)
F30.6692 (7)0.42324 (19)0.6390 (5)0.0780 (16)
F41.3057 (7)0.4580 (2)0.6345 (6)0.0889 (18)
O10.5532 (8)0.26916 (16)1.2410 (4)0.0534 (14)
O21.0003 (10)0.48031 (17)0.8138 (4)0.0649 (17)
N10.5031 (7)0.34346 (17)1.1966 (4)0.0298 (12)
N20.4946 (7)0.38788 (17)1.2406 (5)0.0322 (12)
N30.9873 (7)0.40262 (16)0.8255 (4)0.0290 (12)
N40.9923 (7)0.36189 (17)0.7664 (4)0.0303 (12)
C10.4918 (9)0.4144 (2)1.1501 (6)0.0323 (15)
C20.4947 (9)0.3874 (2)1.0474 (5)0.0304 (14)
C30.5023 (8)0.3431 (2)1.0775 (5)0.0287 (14)
C40.4855 (11)0.4650 (2)1.1623 (6)0.0431 (17)
H4A0.48980.47311.24380.065*
H4B0.36900.47671.12650.065*
H4C0.59360.47851.12470.065*
C50.5039 (10)0.3009 (2)1.0060 (6)0.0380 (16)
H5A0.48850.30920.92500.057*
H5B0.40050.28091.02790.057*
H5C0.62380.28501.01830.057*
C60.5157 (10)0.3064 (2)1.2725 (5)0.0351 (15)
C70.4758 (9)0.3177 (2)1.3954 (5)0.0302 (14)
C80.6131 (9)0.3157 (2)1.4813 (6)0.0362 (16)
C90.5761 (11)0.3226 (2)1.5946 (6)0.0434 (18)
H9A0.67420.32191.65130.052*
C100.3931 (10)0.3306 (2)1.6239 (6)0.0387 (16)
H10A0.36500.33411.70250.046*
C110.2501 (10)0.3337 (2)1.5433 (6)0.0409 (17)
H11A0.12500.34051.56420.049*
C120.2950 (9)0.3266 (2)1.4315 (6)0.0355 (15)
C130.9966 (9)0.3303 (2)0.8459 (6)0.0330 (15)
C140.9948 (9)0.3504 (2)0.9562 (5)0.0325 (15)
C150.9901 (9)0.3960 (2)0.9434 (5)0.0339 (15)
C161.0047 (12)0.2810 (2)0.8158 (7)0.051 (2)
H16A1.02170.27770.73320.076*
H16B0.88720.26610.83690.076*
H16C1.11050.26660.85750.076*
C170.9875 (11)0.4331 (3)1.0304 (6)0.0481 (19)
H17A0.99030.41971.10740.072*
H17B0.87290.45121.01950.072*
H17C1.09770.45271.02170.072*
C180.9919 (10)0.4439 (2)0.7649 (6)0.0378 (16)
C190.9876 (10)0.4396 (2)0.6374 (6)0.0374 (16)
C200.8243 (12)0.4300 (3)0.5776 (7)0.052 (2)
C210.8162 (19)0.4272 (3)0.4604 (8)0.087 (4)
H21A0.70180.42000.42060.105*
C220.975 (2)0.4350 (3)0.4030 (8)0.100 (5)
H22A0.97110.43310.32170.120*
C231.141 (2)0.4456 (4)0.4571 (10)0.090 (4)
H23A1.25080.45120.41480.108*
C241.1454 (13)0.4478 (3)0.5754 (7)0.058 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0507 (5)0.0423 (4)0.0296 (4)−0.0035 (3)0.0003 (3)0.0051 (3)
Br20.0450 (4)0.0693 (6)0.0328 (4)−0.0021 (4)−0.0021 (3)0.0171 (4)
F10.036 (2)0.073 (3)0.067 (3)0.004 (2)0.001 (2)−0.013 (2)
F20.039 (2)0.071 (3)0.041 (2)0.006 (2)−0.0080 (19)−0.004 (2)
F30.055 (3)0.076 (4)0.102 (4)−0.014 (3)−0.013 (3)0.008 (3)
F40.049 (3)0.093 (4)0.126 (5)−0.006 (3)0.018 (3)−0.001 (4)
O10.095 (4)0.021 (2)0.044 (3)0.013 (3)0.016 (3)0.000 (2)
O20.124 (5)0.029 (3)0.042 (3)0.000 (3)0.002 (3)−0.002 (2)
N10.036 (3)0.027 (3)0.026 (3)−0.002 (2)0.001 (2)−0.003 (2)
N20.040 (3)0.024 (3)0.033 (3)0.000 (2)0.002 (2)0.000 (2)
N30.037 (3)0.023 (3)0.027 (3)0.001 (2)0.000 (2)−0.003 (2)
N40.039 (3)0.025 (3)0.027 (3)−0.003 (2)0.001 (2)−0.005 (2)
C10.039 (4)0.025 (3)0.033 (4)−0.001 (3)0.004 (3)0.000 (3)
C20.040 (4)0.028 (3)0.024 (3)0.001 (3)0.007 (3)0.001 (3)
C30.029 (3)0.028 (3)0.029 (3)−0.001 (3)0.004 (3)−0.002 (3)
C40.058 (5)0.027 (4)0.044 (4)−0.007 (3)−0.001 (4)0.000 (3)
C50.047 (4)0.035 (4)0.032 (4)−0.005 (3)0.001 (3)−0.006 (3)
C60.044 (4)0.035 (4)0.027 (4)0.002 (3)0.004 (3)0.002 (3)
C70.041 (4)0.020 (3)0.030 (4)0.000 (3)0.002 (3)0.000 (3)
C80.034 (4)0.027 (3)0.047 (4)0.002 (3)0.001 (3)−0.004 (3)
C90.056 (5)0.043 (4)0.031 (4)−0.006 (3)−0.011 (3)0.000 (3)
C100.053 (5)0.029 (4)0.033 (4)0.002 (3)−0.004 (3)0.005 (3)
C110.038 (4)0.040 (4)0.045 (4)−0.001 (3)0.010 (3)0.000 (3)
C120.036 (4)0.037 (4)0.034 (4)−0.003 (3)−0.001 (3)−0.007 (3)
C130.036 (4)0.025 (3)0.038 (4)−0.003 (3)−0.002 (3)0.000 (3)
C140.033 (4)0.034 (4)0.030 (4)−0.003 (3)0.001 (3)0.002 (3)
C150.040 (4)0.040 (4)0.022 (3)0.004 (3)0.000 (3)−0.004 (3)
C160.072 (5)0.032 (4)0.048 (5)−0.010 (4)0.002 (4)0.005 (3)
C170.063 (5)0.051 (5)0.030 (4)0.002 (4)0.004 (4)−0.014 (3)
C180.053 (4)0.027 (4)0.034 (4)0.009 (3)0.003 (3)−0.004 (3)
C190.055 (4)0.021 (3)0.036 (4)0.006 (3)−0.002 (3)0.003 (3)
C200.067 (6)0.037 (4)0.052 (5)−0.003 (4)−0.008 (4)0.008 (4)
C210.167 (12)0.046 (5)0.047 (6)−0.006 (6)−0.051 (7)0.008 (4)
C220.231 (18)0.044 (6)0.025 (5)0.015 (8)0.011 (8)0.012 (4)
C230.147 (12)0.062 (7)0.065 (7)0.016 (7)0.052 (7)0.016 (6)
C240.072 (6)0.048 (5)0.055 (5)0.000 (4)0.013 (5)0.003 (4)

Geometric parameters (Å, °)

Br1—C21.877 (6)C7—C121.389 (9)
Br2—C141.881 (6)C8—C91.371 (10)
F1—C81.358 (8)C9—C101.375 (10)
F2—C121.363 (8)C9—H9A0.9500
F3—C201.347 (9)C10—C111.370 (10)
F4—C241.351 (10)C10—H10A0.9500
O1—C61.185 (8)C11—C121.368 (9)
O2—C181.210 (8)C11—H11A0.9500
N1—C31.390 (8)C13—C141.416 (9)
N1—N21.401 (7)C13—C161.489 (9)
N1—C61.403 (8)C14—C151.345 (9)
N2—C11.311 (8)C15—C171.487 (9)
N3—N41.380 (7)C16—H16A0.9800
N3—C151.390 (8)C16—H16B0.9800
N3—C181.403 (8)C16—H16C0.9800
N4—C131.311 (8)C17—H17A0.9800
C1—C21.438 (9)C17—H17B0.9800
C1—C41.491 (8)C17—H17C0.9800
C2—C31.346 (9)C18—C191.494 (9)
C3—C51.491 (8)C19—C201.369 (10)
C4—H4A0.9800C19—C241.373 (11)
C4—H4B0.9800C20—C211.371 (12)
C4—H4C0.9800C21—C221.350 (16)
C5—H5A0.9800C21—H21A0.9500
C5—H5B0.9800C22—C231.358 (17)
C5—H5C0.9800C22—H22A0.9500
C6—C71.506 (8)C23—C241.382 (13)
C7—C81.382 (9)C23—H23A0.9500
C3—N1—N2112.0 (5)C10—C11—H11A121.4
C3—N1—C6128.7 (5)F2—C12—C11119.2 (6)
N2—N1—C6119.3 (5)F2—C12—C7116.7 (6)
C1—N2—N1104.8 (5)C11—C12—C7124.1 (6)
N4—N3—C15112.0 (5)N4—C13—C14110.5 (5)
N4—N3—C18119.5 (5)N4—C13—C16121.2 (6)
C15—N3—C18128.3 (5)C14—C13—C16128.3 (6)
C13—N4—N3104.9 (5)C15—C14—C13108.3 (6)
N2—C1—C2110.2 (5)C15—C14—Br2125.1 (5)
N2—C1—C4120.9 (6)C13—C14—Br2126.6 (5)
C2—C1—C4128.9 (6)C14—C15—N3104.4 (5)
C3—C2—C1108.3 (5)C14—C15—C17130.6 (6)
C3—C2—Br1125.9 (5)N3—C15—C17125.1 (6)
C1—C2—Br1125.7 (5)C13—C16—H16A109.5
C2—C3—N1104.7 (5)C13—C16—H16B109.5
C2—C3—C5130.8 (6)H16A—C16—H16B109.5
N1—C3—C5124.5 (6)C13—C16—H16C109.5
C1—C4—H4A109.5H16A—C16—H16C109.5
C1—C4—H4B109.5H16B—C16—H16C109.5
H4A—C4—H4B109.5C15—C17—H17A109.5
C1—C4—H4C109.5C15—C17—H17B109.5
H4A—C4—H4C109.5H17A—C17—H17B109.5
H4B—C4—H4C109.5C15—C17—H17C109.5
C3—C5—H5A109.5H17A—C17—H17C109.5
C3—C5—H5B109.5H17B—C17—H17C109.5
H5A—C5—H5B109.5O2—C18—N3121.6 (6)
C3—C5—H5C109.5O2—C18—C19123.0 (6)
H5A—C5—H5C109.5N3—C18—C19115.4 (5)
H5B—C5—H5C109.5C20—C19—C24117.6 (7)
O1—C6—N1121.9 (6)C20—C19—C18121.3 (7)
O1—C6—C7123.2 (6)C24—C19—C18121.0 (7)
N1—C6—C7114.9 (5)F3—C20—C19117.2 (7)
C8—C7—C12115.5 (6)F3—C20—C21120.6 (9)
C8—C7—C6122.2 (6)C19—C20—C21122.2 (9)
C12—C7—C6122.0 (6)C22—C21—C20118.1 (10)
F1—C8—C9120.4 (6)C22—C21—H21A120.9
F1—C8—C7116.8 (6)C20—C21—H21A120.9
C9—C8—C7122.9 (6)C21—C22—C23122.5 (10)
C8—C9—C10118.3 (7)C21—C22—H22A118.8
C8—C9—H9A120.9C23—C22—H22A118.8
C10—C9—H9A120.9C22—C23—C24118.1 (11)
C11—C10—C9122.1 (7)C22—C23—H23A120.9
C11—C10—H10A119.0C24—C23—H23A120.9
C9—C10—H10A119.0F4—C24—C19117.4 (8)
C12—C11—C10117.2 (7)F4—C24—C23121.2 (9)
C12—C11—H11A121.4C19—C24—C23121.4 (10)
C3—N1—N2—C1−1.0 (7)C8—C7—C12—C111.0 (10)
C6—N1—N2—C1177.4 (6)C6—C7—C12—C11175.0 (6)
C15—N3—N4—C130.5 (7)N3—N4—C13—C14−0.1 (7)
C18—N3—N4—C13176.6 (6)N3—N4—C13—C16−179.4 (6)
N1—N2—C1—C21.1 (7)N4—C13—C14—C15−0.3 (8)
N1—N2—C1—C4−179.2 (6)C16—C13—C14—C15178.9 (7)
N2—C1—C2—C3−0.9 (8)N4—C13—C14—Br2−179.3 (5)
C4—C1—C2—C3179.4 (7)C16—C13—C14—Br2−0.1 (11)
N2—C1—C2—Br1178.8 (5)C13—C14—C15—N30.6 (7)
C4—C1—C2—Br1−0.9 (11)Br2—C14—C15—N3179.6 (4)
C1—C2—C3—N10.3 (7)C13—C14—C15—C17−179.6 (7)
Br1—C2—C3—N1−179.4 (4)Br2—C14—C15—C17−0.6 (11)
C1—C2—C3—C5178.5 (6)N4—N3—C15—C14−0.7 (7)
Br1—C2—C3—C5−1.2 (11)C18—N3—C15—C14−176.4 (6)
N2—N1—C3—C20.4 (7)N4—N3—C15—C17179.5 (6)
C6—N1—C3—C2−177.8 (6)C18—N3—C15—C173.8 (11)
N2—N1—C3—C5−177.9 (6)N4—N3—C18—O2−175.1 (7)
C6—N1—C3—C53.8 (10)C15—N3—C18—O20.3 (11)
C3—N1—C6—O110.4 (11)N4—N3—C18—C194.4 (9)
N2—N1—C6—O1−167.7 (6)C15—N3—C18—C19179.8 (6)
C3—N1—C6—C7−168.9 (6)O2—C18—C19—C20−103.7 (9)
N2—N1—C6—C713.0 (8)N3—C18—C19—C2076.9 (8)
O1—C6—C7—C867.7 (10)O2—C18—C19—C2472.5 (10)
N1—C6—C7—C8−113.0 (7)N3—C18—C19—C24−107.0 (8)
O1—C6—C7—C12−105.9 (8)C24—C19—C20—F3−178.2 (7)
N1—C6—C7—C1273.4 (8)C18—C19—C20—F3−2.0 (10)
C12—C7—C8—F1179.5 (6)C24—C19—C20—C211.8 (11)
C6—C7—C8—F15.5 (9)C18—C19—C20—C21178.1 (7)
C12—C7—C8—C9−1.1 (9)F3—C20—C21—C22179.0 (8)
C6—C7—C8—C9−175.1 (6)C19—C20—C21—C22−1.1 (13)
F1—C8—C9—C10−178.6 (6)C20—C21—C22—C23−0.2 (16)
C7—C8—C9—C102.0 (10)C21—C22—C23—C240.6 (16)
C8—C9—C10—C11−2.8 (10)C20—C19—C24—F4179.0 (7)
C9—C10—C11—C122.6 (10)C18—C19—C24—F42.7 (11)
C10—C11—C12—F2−179.8 (6)C20—C19—C24—C23−1.3 (12)
C10—C11—C12—C7−1.7 (10)C18—C19—C24—C23−177.6 (8)
C8—C7—C12—F2179.0 (6)C22—C23—C24—F4179.9 (9)
C6—C7—C12—F2−7.0 (9)C22—C23—C24—C190.2 (14)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5260).

References

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