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Acta Crystallogr Sect E Struct Rep Online. 2008 March 1; 64(Pt 3): o646.
Published online 2008 February 29. doi:  10.1107/S1600536808005539
PMCID: PMC2960867

4-Bromo-1-[2,6-dichloro-4-(trifluoro­meth­yl)phen­yl]-5-(4-methoxy­benzyl­ideneamino)-1H-pyrazole-3-carbonitrile

Abstract

The title compound, C19H10BrCl2F3N4O, is an imine with an overall Y shape. The dihedral angles between the pyrazole ring and the methoxy- and trifluoromethyl-substituted benzene ring planes are 88.4 (2) and 65.8 (2)°, respectively.

Related literature

For the insecticidal properties of similar compounds, see: Philippe (1997 [triangle], 2000 [triangle]). For a related structure, see: Zhong et al. (2005 [triangle]).

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Object name is e-64-0o646-scheme1.jpg

Experimental

Crystal data

  • C19H10BrCl2F3N4O
  • M r = 518.12
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o646-efi1.jpg
  • a = 10.215 (7) Å
  • b = 13.407 (9) Å
  • c = 15.108 (11) Å
  • β = 94.634 (13)°
  • V = 2062 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.30 mm−1
  • T = 293 (2) K
  • 0.28 × 0.25 × 0.23 mm

Data collection

  • Bruker P4/SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2002 [triangle]) T min = 0.568, T max = 0.618
  • 15375 measured reflections
  • 4681 independent reflections
  • 4061 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.160
  • S = 1.02
  • 4681 reflections
  • 271 parameters
  • H-atom parameters constrained
  • Δρmax = 0.87 e Å−3
  • Δρmin = −1.22 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005539/sj2465sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005539/sj2465Isup2.hkl

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

Acknowledgments

This work was supported by the National Natural Science Foundation of Fujian Province (No. B0610033).

supplementary crystallographic information

Comment

The title compound, (I), (Fig. 1) is similar to the very effective insecticides used to treat animals such as cows and sheep (Philippe, 1997, 2000) and its structure is reported here, Fig 1. The molecule contains three essentially planar rings and the dihedral angles between the pyrazole ring (C1—C3, N2, N3) and the ring planes of the (C5—C7) and (C13—C17) benzene rings are 88.4 (2)° and 65.8 (2)°, respectively.

Experimental

The title compound was prepared by literature methods (Zhong et al., 2005, Philippe, 2000). Colourless single crystals suitable for X-ray analysis were obtained by slow evaporation of an anhydrous ethanol-acetone (2:1) solution of (I) (m.p. 435–437 K).

Refinement

All H atoms were initially located in a difference Fourier map but were eventually placed in their geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 Å, and with Uiso(H) = 1.2eq(C) and 0.96 Å, Uiso = 1.5Ueq (C) for CH3 atoms. The low Ueq of C11 as compared to its neighbours may be attributed to the high displacement parameters for atoms F1, F2 and F3, indicating either large thermal motion or rotational disorder of the trifluoromethyl group. However, attempts to represent the CF3 group using a disorder model were unsuccessful.

Figures

Fig. 1.
The molecular structure of (I) showing the atom numbering scheme and displacement ellipsoids at the 30% probability level.

Crystal data

C19H10BrCl2F3N4OF000 = 1024
Mr = 518.12Dx = 1.669 Mg m3
Monoclinic, P21/cMelting point = 435–437 K
Hall symbol: -P 2ybcMo Kα radiation λ = 0.71073 Å
a = 10.215 (7) ÅCell parameters from 3780 reflections
b = 13.407 (9) Åθ = 2.6–24.2º
c = 15.108 (11) ŵ = 2.30 mm1
β = 94.634 (13)ºT = 293 (2) K
V = 2062 (2) Å3Block, colorless
Z = 40.28 × 0.25 × 0.23 mm

Data collection

Bruker P4 CCD diffractometer4681 independent reflections
Radiation source: fine-focus sealed tube4061 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.028
T = 293(2) Kθmax = 27.6º
ω scansθmin = 2.8º
Absorption correction: multi-scan(SADABS; Bruker, 2002)h = −13→10
Tmin = 0.568, Tmax = 0.618k = −17→17
15375 measured reflectionsl = −19→19

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.160  w = 1/[σ2(Fo2) + (0.1058P)2 + 1.2139P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
4681 reflectionsΔρmax = 0.87 e Å3
271 parametersΔρmin = −1.22 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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
Br10.47949 (4)0.47599 (2)0.18806 (3)0.06204 (17)
Cl10.47167 (9)0.15617 (7)−0.07867 (6)0.0635 (3)
Cl20.21780 (9)0.09133 (6)0.21206 (5)0.0598 (2)
O1−0.1317 (3)0.5592 (2)−0.2291 (2)0.0705 (7)
N10.7437 (3)0.2820 (3)0.3107 (3)0.0722 (9)
N20.5089 (2)0.17560 (18)0.16494 (16)0.0440 (5)
N30.4063 (2)0.19538 (16)0.10558 (15)0.0401 (5)
N40.2718 (2)0.32184 (17)0.03993 (16)0.0440 (5)
C10.5457 (3)0.2656 (2)0.19544 (18)0.0426 (6)
C20.4669 (3)0.34164 (19)0.1561 (2)0.0431 (6)
C30.3773 (3)0.29447 (18)0.09722 (18)0.0393 (5)
C40.6555 (3)0.2745 (2)0.2597 (2)0.0510 (7)
C50.3380 (3)0.11449 (18)0.06234 (17)0.0372 (5)
C60.2496 (3)0.0587 (2)0.10637 (18)0.0404 (5)
C70.1868 (3)−0.02304 (19)0.0660 (2)0.0455 (6)
H70.1275−0.06030.09590.055*
C80.2134 (3)−0.0482 (2)−0.0186 (2)0.0444 (6)
C90.2998 (3)0.0065 (2)−0.0649 (2)0.0467 (6)
H90.3161−0.0110−0.12250.056*
C100.3616 (3)0.0880 (2)−0.02374 (18)0.0412 (5)
C110.1513 (4)−0.1404 (2)−0.0601 (3)0.0606 (8)
C120.2714 (3)0.4090 (2)0.0053 (2)0.0468 (6)
H120.34330.45030.01940.056*
C130.1648 (3)0.4469 (2)−0.05455 (19)0.0423 (6)
C140.1740 (3)0.5440 (2)−0.0862 (2)0.0499 (7)
H140.24730.5823−0.06820.060*
C150.0759 (3)0.5846 (2)−0.1438 (2)0.0485 (6)
H150.08260.6499−0.16370.058*
C16−0.0316 (3)0.5275 (2)−0.1712 (2)0.0474 (6)
C17−0.0425 (3)0.4296 (3)−0.1403 (2)0.0556 (7)
H17−0.11570.3913−0.15860.067*
C180.0549 (3)0.3903 (2)−0.0829 (2)0.0499 (7)
H180.04760.3252−0.06270.060*
C19−0.1250 (5)0.6581 (3)−0.2612 (4)0.0878 (15)
H19C−0.20050.6714−0.30150.132*
H19B−0.04670.6660−0.29160.132*
H19A−0.12330.7039−0.21230.132*
F10.2269 (3)−0.21908 (16)−0.0449 (2)0.0972 (10)
F20.0391 (3)−0.1633 (2)−0.0287 (3)0.1064 (11)
F30.1310 (4)−0.1354 (3)−0.1460 (2)0.1269 (15)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0722 (3)0.0340 (2)0.0776 (3)−0.00455 (12)−0.00746 (19)−0.01343 (13)
Cl10.0740 (5)0.0690 (5)0.0497 (4)−0.0276 (4)0.0184 (4)−0.0037 (3)
Cl20.0782 (5)0.0583 (5)0.0453 (4)0.0063 (4)0.0197 (4)0.0037 (3)
O10.0646 (15)0.0602 (15)0.0822 (18)0.0061 (12)−0.0225 (13)0.0004 (13)
N10.0669 (19)0.0670 (19)0.079 (2)0.0077 (15)−0.0188 (17)−0.0201 (16)
N20.0514 (13)0.0380 (12)0.0416 (11)0.0037 (10)−0.0028 (10)−0.0017 (9)
N30.0520 (12)0.0308 (10)0.0366 (10)−0.0008 (9)−0.0025 (9)−0.0019 (8)
N40.0547 (13)0.0327 (11)0.0434 (12)0.0007 (9)−0.0037 (10)−0.0006 (9)
C10.0483 (14)0.0377 (13)0.0412 (13)0.0013 (10)0.0008 (11)−0.0060 (10)
C20.0517 (15)0.0309 (12)0.0460 (14)−0.0012 (10)−0.0002 (11)−0.0049 (10)
C30.0478 (13)0.0294 (11)0.0407 (13)−0.0014 (10)0.0045 (10)−0.0017 (9)
C40.0555 (17)0.0464 (15)0.0501 (16)0.0048 (12)−0.0012 (13)−0.0126 (12)
C50.0458 (13)0.0271 (11)0.0381 (12)0.0005 (9)0.0002 (10)−0.0006 (9)
C60.0481 (14)0.0325 (12)0.0410 (13)0.0050 (10)0.0052 (11)0.0046 (10)
C70.0440 (14)0.0331 (13)0.0596 (17)−0.0016 (10)0.0057 (12)0.0084 (11)
C80.0461 (14)0.0305 (12)0.0551 (16)−0.0028 (10)−0.0045 (12)−0.0017 (11)
C90.0571 (16)0.0409 (13)0.0419 (14)−0.0053 (12)0.0019 (12)−0.0070 (11)
C100.0477 (14)0.0372 (13)0.0392 (13)−0.0059 (10)0.0053 (10)−0.0023 (10)
C110.0627 (19)0.0413 (16)0.075 (2)−0.0116 (14)−0.0131 (16)−0.0049 (15)
C120.0539 (16)0.0358 (13)0.0498 (15)−0.0028 (11)−0.0012 (12)0.0000 (11)
C130.0527 (15)0.0331 (12)0.0407 (13)−0.0004 (11)0.0027 (11)−0.0002 (10)
C140.0570 (17)0.0344 (13)0.0567 (17)−0.0059 (12)−0.0056 (13)0.0023 (12)
C150.0604 (17)0.0320 (12)0.0522 (16)0.0032 (11)−0.0007 (13)0.0019 (11)
C160.0513 (16)0.0440 (16)0.0461 (15)0.0069 (11)−0.0005 (12)−0.0038 (11)
C170.0546 (17)0.0481 (17)0.0628 (19)−0.0122 (13)−0.0031 (14)−0.0011 (14)
C180.0614 (17)0.0363 (13)0.0522 (16)−0.0082 (12)0.0061 (13)0.0024 (11)
C190.091 (3)0.059 (2)0.106 (4)0.020 (2)−0.035 (3)0.006 (2)
F10.0977 (18)0.0389 (11)0.150 (3)0.0004 (11)−0.0223 (18)−0.0259 (14)
F20.0762 (16)0.0812 (18)0.164 (3)−0.0395 (14)0.0210 (18)−0.0324 (19)
F30.198 (4)0.095 (2)0.0784 (18)−0.074 (2)−0.044 (2)−0.0037 (16)

Geometric parameters (Å, °)

Br1—C21.867 (3)C8—C111.503 (4)
Cl1—C101.714 (3)C9—C101.384 (4)
Cl2—C61.712 (3)C9—H90.9300
O1—C161.359 (4)C11—F31.299 (5)
O1—C191.416 (5)C11—F21.311 (5)
N1—C41.142 (5)C11—F11.317 (4)
N2—C11.334 (4)C12—C131.450 (4)
N2—N31.349 (3)C12—H120.9300
N3—C31.365 (3)C13—C181.393 (4)
N3—C51.420 (3)C13—C141.393 (4)
N4—C121.280 (4)C14—C151.385 (4)
N4—C31.376 (4)C14—H140.9300
C1—C21.402 (4)C15—C161.374 (5)
C1—C41.428 (4)C15—H150.9300
C2—C31.377 (4)C16—C171.401 (5)
C5—C61.383 (4)C17—C181.370 (5)
C5—C101.388 (4)C17—H170.9300
C6—C71.386 (4)C18—H180.9300
C7—C81.371 (5)C19—H19C0.9600
C7—H70.9300C19—H19B0.9600
C8—C91.380 (4)C19—H19A0.9600
C16—O1—C19117.3 (3)F3—C11—F2107.5 (3)
C1—N2—N3103.5 (2)F3—C11—F1105.0 (4)
N2—N3—C3113.8 (2)F2—C11—F1105.5 (3)
N2—N3—C5118.8 (2)F3—C11—C8113.7 (3)
C3—N3—C5127.3 (2)F2—C11—C8113.2 (3)
C12—N4—C3118.5 (3)F1—C11—C8111.4 (3)
N2—C1—C2112.0 (2)N4—C12—C13123.5 (3)
N2—C1—C4119.7 (3)N4—C12—H12118.3
C2—C1—C4128.3 (3)C13—C12—H12118.3
C3—C2—C1105.6 (2)C18—C13—C14118.6 (3)
C3—C2—Br1129.7 (2)C18—C13—C12123.2 (3)
C1—C2—Br1124.6 (2)C14—C13—C12118.2 (3)
N3—C3—N4118.1 (2)C15—C14—C13121.1 (3)
N3—C3—C2105.0 (2)C15—C14—H14119.4
N4—C3—C2136.8 (2)C13—C14—H14119.4
N1—C4—C1179.6 (5)C16—C15—C14119.4 (3)
C6—C5—C10118.8 (2)C16—C15—H15120.3
C6—C5—N3120.5 (2)C14—C15—H15120.3
C10—C5—N3120.7 (2)O1—C16—C15124.1 (3)
C5—C6—C7120.8 (3)O1—C16—C17115.5 (3)
C5—C6—Cl2119.4 (2)C15—C16—C17120.3 (3)
C7—C6—Cl2119.8 (2)C18—C17—C16119.8 (3)
C8—C7—C6119.1 (3)C18—C17—H17120.1
C8—C7—H7120.5C16—C17—H17120.1
C6—C7—H7120.5C17—C18—C13120.8 (3)
C7—C8—C9121.6 (3)C17—C18—H18119.6
C7—C8—C11118.9 (3)C13—C18—H18119.6
C9—C8—C11119.5 (3)O1—C19—H19C109.5
C8—C9—C10118.7 (3)O1—C19—H19B109.5
C8—C9—H9120.7H19C—C19—H19B109.5
C10—C9—H9120.7O1—C19—H19A109.5
C9—C10—C5121.0 (2)H19C—C19—H19A109.5
C9—C10—Cl1119.8 (2)H19B—C19—H19A109.5
C5—C10—Cl1119.2 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2465).

References

  • Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Winsonsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Philippe, J. (1997). US Patent No. 6 001 384.
  • Philippe, J. (2000). US Patent No. 6 096 329.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhong, P., Yang, Z. & Shi, Q. (2005). Acta Cryst. E61, o786–o787.

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