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Acta Cryst. (2010). E66, o115    [ doi:10.1107/S1600536809052532 ]

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

X.-D. Mei, Y.-H. Liang and Z.-Y. Wang

Abstract top

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 [pi]-[pi] stacking [centroid-centroid separation = 3.696 (5) Å] helps to establish the packing.

Related literature top

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

Experimental top

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 top

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).

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); 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: SHELX97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids and atom-numbering scheme.
(4-Bromo-3,5-dimethyl-1H-pyrazol-1-yl)(2,6-difluorophenyl)methanone top
Crystal data top
C12H9BrF2N2OF(000) = 1248
Mr = 315.12Dx = 1.720 Mg m−3
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 mm−1
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 top
Rigaku Saturn724+ CCD
diffractometer		4276 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 top
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 = 1.27 w = 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 Å−3
0 restraintsΔρmin = −0.47 e Å−3
Crystal data top
C12H9BrF2N2OV = 2433.5 (15) Å3
Mr = 315.12Z = 8
Monoclinic, P21/cMo Kα radiation
a = 7.116 (3) ŵ = 3.39 mm−1
b = 29.304 (10) ÅT = 173 K
c = 11.674 (4) Å0.17 × 0.17 × 0.17 mm
β = 91.533 (5)°
Data collection top
Rigaku Saturn724+ CCD
diffractometer		4276 independent reflections
Absorption correction: numerical
(CrystalClear; Rigaku, 2008)		3819 reflections with I > 2σ(I)
Tmin = 0.596, Tmax = 0.596Rint = 0.060
15188 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.077H-atom parameters constrained
wR(F2) = 0.158Δρmax = 1.08 e Å−3
S = 1.27Δρmin = −0.47 e Å−3
4276 reflectionsAbsolute structure: ?
329 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
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) top
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, °) top
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)
Acknowledgements top

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).

references
References top

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