Acta Cryst. (2008). E64, o645 [ doi:10.1107/S160053680800545X ]
The title compound, C18H7BrCl2F3N5O2, is an L-shaped tricyclic imine. The pyrazole ring is essentially coplanar with the nitro-substituted benzene ring [dihedral angle = 3.6 (2)°] and approximately perpendicular to the trifluoromethylsubstituted ring [dihedral angle = 88.5 (2)°].
The method of Zhong et al. (2005) was used to prepare 5-amino- 3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]pyrazole(2.5 mmol). This was followed by reaction with 4-nitrobenzaldehyde(2.5 mmol) and hydrochloric acid(2 ml) in anhydrous ethanol(5 ml) to obtain 1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-3-cyano- 5-[(4-nitrophenyl)methyleneamino]-1H-pyrazole, which was then reacted with N-bromosuccinimide(1.5 mmol) (Philippe, 2000) in acetonitrile (6 mL) at room temperature. After being stirred a few minutes, the reaction was monitored by TLC until all starting materials were consumed. Finally, the reaction mixture was evaporated under reduced pressure to provide the required crude product, which was then partitioned between dichloromethane and water. Seperating and drying the organic phase and evaporating it under reduced pressure gave the title compound (88.5% yield). 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. 463–465 K). IR (KBr, ν cm-1): 3396, 2244, 1623, 1596, 1525, 1384, 1310, 1135, 877, 817; 1H NMR (C3D6O, δ, p.p.m.): 9.60 (s, 1H), 8.34 (s, 2H), 8.16(d, 2H), 8.13 (d, 2H); 13C NMR (C3D6O, δ, p.p.m.): 166.4, 151.5, 147.7, 140.7, 137.4, 136.4, 134.6 (q, J = 34.1 Hz), 131.4(2 C), 130.3, 127.2 (2 C), 127.1 (2 C), 124.9(2 C), 121.4 (q, J = 271.1 Hz), 112.3.
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). The low Ueq of C1 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 disordered model were unsuccessful.
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./fl2181fig1thm.gif)
| Fig. 1. The molecular structure of (I) showing the atom numbering scheme and displacement ellipsoids at 50% probability level. |
| C18H7BrCl2F3N5O2 | F000 = 1048 |
| Mr = 533.10 | Dx = 1.732 Mg m−3 |
| Monoclinic, P21/n | Melting point = 463–465 K |
| Hall symbol: -P 2yn | Mo Kα radiation λ = 0.71073 Å |
| a = 8.0925 (7) Å | Cell parameters from 3580 reflections |
| b = 13.0406 (10) Å | θ = 2.6–24.2º |
| c = 19.7165 (16) Å | µ = 2.33 mm−1 |
| β = 100.753 (2)º | T = 298 (2) K |
| V = 2044.2 (3) Å3 | Blcok, colorless |
| Z = 4 | 0.27 × 0.24 × 0.22 mm |
| Bruker APEX area-detector diffractometer | 4437 independent reflections |
| Radiation source: fine-focus sealed tube | 3331 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.024 |
| T = 298(2) K | θmax = 27.0º |
| φ and ω scans | θmin = 1.9º |
| Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −7→10 |
| Tmin = 0.572, Tmax = 0.629 | k = −15→16 |
| 12155 measured reflections | l = −25→19 |
| 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)] = 0.041 | H-atom parameters constrained |
| wR(F2) = 0.110 | w = 1/[σ2(Fo2) + (0.059P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.07 | (Δ/σ)max = 0.004 |
| 4437 reflections | Δρmax = 0.56 e Å−3 |
| 280 parameters | Δρmin = −0.38 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C18H7BrCl2F3N5O2 | V = 2044.2 (3) Å3 |
| Mr = 533.10 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 8.0925 (7) Å | µ = 2.33 mm−1 |
| b = 13.0406 (10) Å | T = 298 (2) K |
| c = 19.7165 (16) Å | 0.27 × 0.24 × 0.22 mm |
| β = 100.753 (2)º |
| Bruker APEX area-detector diffractometer | 4437 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2002) | 3331 reflections with I > 2σ(I) |
| Tmin = 0.572, Tmax = 0.629 | Rint = 0.024 |
| 12155 measured reflections |
| R[F2 > 2σ(F2)] = 0.041 | 280 parameters |
| wR(F2) = 0.110 | H-atom parameters constrained |
| S = 1.07 | Δρmax = 0.56 e Å−3 |
| 4437 reflections | Δρmin = −0.38 e Å−3 |
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 | ||
| Br1 | −0.24016 (4) | 0.51690 (2) | 0.761142 (16) | 0.05284 (13) | |
| Cl1 | 0.30689 (11) | 0.82810 (7) | 0.73346 (4) | 0.0691 (2) | |
| Cl2 | −0.11238 (11) | 0.88488 (7) | 0.91210 (4) | 0.0726 (3) | |
| F1 | 0.5843 (3) | 1.0868 (2) | 0.92604 (16) | 0.1220 (10) | |
| F2 | 0.3925 (4) | 1.19099 (18) | 0.89073 (15) | 0.1444 (13) | |
| F3 | 0.4114 (4) | 1.12171 (18) | 0.98766 (12) | 0.1088 (9) | |
| O1 | 0.5960 (3) | 0.4599 (3) | 1.17024 (13) | 0.0896 (8) | |
| O2 | 0.4901 (5) | 0.3126 (3) | 1.14333 (19) | 0.1335 (14) | |
| N1 | 0.0002 (3) | 0.78718 (16) | 0.79313 (11) | 0.0449 (5) | |
| N2 | −0.1070 (3) | 0.81212 (17) | 0.73411 (12) | 0.0509 (6) | |
| N3 | −0.4315 (4) | 0.7201 (2) | 0.61178 (18) | 0.0856 (10) | |
| N4 | 0.0797 (3) | 0.65801 (17) | 0.87633 (11) | 0.0467 (5) | |
| N5 | 0.4987 (4) | 0.4039 (3) | 1.13390 (16) | 0.0754 (8) | |
| C1 | 0.4224 (5) | 1.1057 (3) | 0.92265 (17) | 0.0655 (9) | |
| C2 | 0.3130 (4) | 1.0194 (2) | 0.89024 (15) | 0.0510 (7) | |
| C3 | 0.3571 (4) | 0.9687 (2) | 0.83475 (15) | 0.0538 (7) | |
| H3 | 0.4544 | 0.9866 | 0.8189 | 0.065* | |
| C4 | 0.2546 (4) | 0.8908 (2) | 0.80309 (13) | 0.0469 (6) | |
| C5 | 0.1103 (3) | 0.86405 (19) | 0.82729 (13) | 0.0437 (6) | |
| C6 | 0.0705 (3) | 0.9163 (2) | 0.88322 (14) | 0.0488 (6) | |
| C7 | 0.1700 (4) | 0.9942 (2) | 0.91509 (16) | 0.0521 (7) | |
| H7 | 0.1417 | 1.0290 | 0.9525 | 0.062* | |
| C8 | −0.3258 (4) | 0.7239 (2) | 0.65789 (17) | 0.0581 (8) | |
| C9 | −0.1943 (4) | 0.7263 (2) | 0.71809 (14) | 0.0469 (6) | |
| C10 | −0.1445 (3) | 0.6474 (2) | 0.76518 (14) | 0.0436 (6) | |
| C11 | −0.0177 (3) | 0.6883 (2) | 0.81450 (13) | 0.0427 (6) | |
| C12 | 0.0866 (4) | 0.5653 (2) | 0.89369 (15) | 0.0538 (7) | |
| H12 | 0.0246 | 0.5182 | 0.8638 | 0.065* | |
| C13 | 0.1866 (4) | 0.5268 (2) | 0.95842 (15) | 0.0482 (7) | |
| C14 | 0.1918 (4) | 0.4225 (2) | 0.96947 (17) | 0.0607 (8) | |
| H14 | 0.1278 | 0.3790 | 0.9375 | 0.073* | |
| C15 | 0.2915 (4) | 0.3823 (3) | 1.02788 (18) | 0.0652 (9) | |
| H15 | 0.2954 | 0.3119 | 1.0357 | 0.078* | |
| C16 | 0.3844 (4) | 0.4479 (3) | 1.07395 (15) | 0.0546 (7) | |
| C17 | 0.3788 (4) | 0.5522 (3) | 1.06511 (15) | 0.0578 (7) | |
| H17 | 0.4417 | 0.5952 | 1.0977 | 0.069* | |
| C18 | 0.2781 (4) | 0.5918 (2) | 1.00707 (15) | 0.0535 (7) | |
| H18 | 0.2714 | 0.6624 | 1.0005 | 0.064* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0565 (2) | 0.04456 (18) | 0.0567 (2) | −0.00804 (13) | 0.00875 (13) | −0.00358 (13) |
| Cl1 | 0.0809 (6) | 0.0743 (6) | 0.0569 (5) | 0.0042 (5) | 0.0252 (4) | −0.0109 (4) |
| Cl2 | 0.0723 (5) | 0.0821 (6) | 0.0717 (5) | −0.0225 (4) | 0.0347 (4) | −0.0172 (4) |
| F1 | 0.0760 (16) | 0.126 (2) | 0.158 (3) | −0.0348 (16) | 0.0070 (15) | −0.0421 (19) |
| F2 | 0.199 (3) | 0.0628 (14) | 0.136 (2) | −0.0535 (17) | −0.061 (2) | 0.0372 (15) |
| F3 | 0.145 (2) | 0.1075 (18) | 0.0751 (15) | −0.0630 (17) | 0.0242 (14) | −0.0331 (13) |
| O1 | 0.0723 (17) | 0.137 (3) | 0.0546 (15) | 0.0176 (17) | 0.0000 (13) | 0.0003 (17) |
| O2 | 0.166 (3) | 0.101 (2) | 0.113 (3) | 0.027 (2) | −0.026 (2) | 0.045 (2) |
| N1 | 0.0517 (13) | 0.0395 (12) | 0.0419 (12) | −0.0013 (10) | 0.0048 (10) | 0.0010 (9) |
| N2 | 0.0591 (15) | 0.0435 (13) | 0.0465 (13) | 0.0051 (11) | 0.0004 (11) | −0.0022 (10) |
| N3 | 0.081 (2) | 0.080 (2) | 0.082 (2) | 0.0017 (17) | −0.0216 (18) | 0.0013 (17) |
| N4 | 0.0533 (13) | 0.0445 (13) | 0.0422 (12) | −0.0015 (11) | 0.0084 (10) | 0.0041 (10) |
| N5 | 0.077 (2) | 0.093 (2) | 0.0571 (18) | 0.0245 (19) | 0.0151 (15) | 0.0174 (18) |
| C1 | 0.073 (2) | 0.062 (2) | 0.059 (2) | −0.0211 (17) | 0.0039 (16) | 0.0027 (16) |
| C2 | 0.0598 (19) | 0.0473 (15) | 0.0438 (16) | −0.0091 (13) | 0.0048 (13) | 0.0050 (13) |
| C3 | 0.0537 (18) | 0.0585 (18) | 0.0501 (17) | −0.0082 (14) | 0.0125 (13) | 0.0068 (14) |
| C4 | 0.0545 (16) | 0.0482 (16) | 0.0383 (14) | 0.0027 (13) | 0.0094 (12) | 0.0007 (12) |
| C5 | 0.0527 (16) | 0.0368 (14) | 0.0400 (14) | −0.0006 (12) | 0.0050 (11) | 0.0003 (11) |
| C6 | 0.0515 (16) | 0.0502 (16) | 0.0454 (15) | −0.0058 (13) | 0.0110 (12) | −0.0012 (12) |
| C7 | 0.0639 (19) | 0.0473 (16) | 0.0452 (17) | −0.0051 (13) | 0.0107 (14) | −0.0064 (12) |
| C8 | 0.0629 (19) | 0.0487 (17) | 0.0580 (19) | 0.0000 (14) | −0.0008 (16) | −0.0009 (14) |
| C9 | 0.0501 (16) | 0.0427 (15) | 0.0466 (16) | 0.0030 (13) | 0.0056 (12) | −0.0041 (12) |
| C10 | 0.0467 (15) | 0.0389 (14) | 0.0454 (15) | −0.0012 (12) | 0.0092 (11) | −0.0040 (11) |
| C11 | 0.0499 (15) | 0.0367 (13) | 0.0437 (15) | 0.0006 (12) | 0.0142 (12) | 0.0011 (11) |
| C12 | 0.0571 (18) | 0.0459 (16) | 0.0546 (18) | −0.0024 (14) | 0.0008 (13) | 0.0003 (13) |
| C13 | 0.0485 (16) | 0.0471 (16) | 0.0487 (16) | −0.0013 (13) | 0.0085 (12) | 0.0050 (13) |
| C14 | 0.0630 (19) | 0.0482 (17) | 0.066 (2) | −0.0078 (15) | −0.0009 (15) | 0.0060 (14) |
| C15 | 0.073 (2) | 0.0504 (18) | 0.073 (2) | 0.0031 (16) | 0.0138 (17) | 0.0167 (16) |
| C16 | 0.0543 (17) | 0.0666 (19) | 0.0442 (16) | 0.0074 (15) | 0.0126 (13) | 0.0091 (14) |
| C17 | 0.0634 (19) | 0.0645 (19) | 0.0441 (16) | 0.0011 (16) | 0.0067 (13) | −0.0040 (14) |
| C18 | 0.0657 (19) | 0.0458 (16) | 0.0490 (17) | 0.0014 (14) | 0.0106 (14) | −0.0009 (13) |
| Br1—C10 | 1.865 (3) | C3—H3 | 0.9300 |
| Cl1—C4 | 1.717 (3) | C4—C5 | 1.386 (4) |
| Cl2—C6 | 1.731 (3) | C5—C6 | 1.384 (4) |
| F1—C1 | 1.322 (4) | C6—C7 | 1.374 (4) |
| F2—C1 | 1.279 (4) | C7—H7 | 0.9300 |
| F3—C1 | 1.318 (4) | C8—C9 | 1.439 (4) |
| O1—N5 | 1.206 (4) | C9—C10 | 1.394 (4) |
| O2—N5 | 1.209 (4) | C10—C11 | 1.382 (4) |
| N1—N2 | 1.355 (3) | C12—C13 | 1.466 (4) |
| N1—C11 | 1.373 (3) | C12—H12 | 0.9300 |
| N1—C5 | 1.424 (3) | C13—C14 | 1.378 (4) |
| N2—C9 | 1.330 (3) | C13—C18 | 1.386 (4) |
| N3—C8 | 1.127 (4) | C14—C15 | 1.380 (4) |
| N4—C12 | 1.256 (3) | C14—H14 | 0.9300 |
| N4—C11 | 1.380 (3) | C15—C16 | 1.366 (5) |
| N5—C16 | 1.474 (4) | C15—H15 | 0.9300 |
| C1—C2 | 1.499 (4) | C16—C17 | 1.371 (5) |
| C2—C7 | 1.377 (5) | C17—C18 | 1.375 (4) |
| C2—C3 | 1.381 (4) | C17—H17 | 0.9300 |
| C3—C4 | 1.384 (4) | C18—H18 | 0.9300 |
| N2—N1—C11 | 113.7 (2) | N3—C8—C9 | 177.9 (4) |
| N2—N1—C5 | 118.7 (2) | N2—C9—C10 | 112.8 (2) |
| C11—N1—C5 | 127.5 (2) | N2—C9—C8 | 119.5 (2) |
| C9—N2—N1 | 103.2 (2) | C10—C9—C8 | 127.6 (3) |
| C12—N4—C11 | 120.3 (2) | C11—C10—C9 | 105.6 (2) |
| O1—N5—O2 | 123.7 (3) | C11—C10—Br1 | 129.0 (2) |
| O1—N5—C16 | 118.9 (3) | C9—C10—Br1 | 125.4 (2) |
| O2—N5—C16 | 117.4 (4) | N1—C11—N4 | 117.6 (2) |
| F2—C1—F3 | 107.5 (3) | N1—C11—C10 | 104.7 (2) |
| F2—C1—F1 | 106.3 (3) | N4—C11—C10 | 137.6 (2) |
| F3—C1—F1 | 103.1 (3) | N4—C12—C13 | 123.8 (3) |
| F2—C1—C2 | 113.6 (3) | N4—C12—H12 | 118.1 |
| F3—C1—C2 | 113.1 (3) | C13—C12—H12 | 118.1 |
| F1—C1—C2 | 112.5 (3) | C14—C13—C18 | 119.8 (3) |
| C7—C2—C3 | 121.7 (3) | C14—C13—C12 | 118.1 (3) |
| C7—C2—C1 | 119.7 (3) | C18—C13—C12 | 122.1 (3) |
| C3—C2—C1 | 118.5 (3) | C13—C14—C15 | 120.2 (3) |
| C2—C3—C4 | 119.1 (3) | C13—C14—H14 | 119.9 |
| C2—C3—H3 | 120.4 | C15—C14—H14 | 119.9 |
| C4—C3—H3 | 120.4 | C16—C15—C14 | 118.7 (3) |
| C3—C4—C5 | 120.1 (3) | C16—C15—H15 | 120.6 |
| C3—C4—Cl1 | 119.6 (2) | C14—C15—H15 | 120.6 |
| C5—C4—Cl1 | 120.3 (2) | C15—C16—C17 | 122.4 (3) |
| C6—C5—C4 | 119.1 (2) | C15—C16—N5 | 118.3 (3) |
| C6—C5—N1 | 120.4 (2) | C17—C16—N5 | 119.2 (3) |
| C4—C5—N1 | 120.5 (2) | C16—C17—C18 | 118.6 (3) |
| C7—C6—C5 | 121.6 (3) | C16—C17—H17 | 120.7 |
| C7—C6—Cl2 | 119.3 (2) | C18—C17—H17 | 120.7 |
| C5—C6—Cl2 | 119.1 (2) | C17—C18—C13 | 120.2 (3) |
| C6—C7—C2 | 118.3 (3) | C17—C18—H18 | 119.9 |
| C6—C7—H7 | 120.9 | C13—C18—H18 | 119.9 |
| C2—C7—H7 | 120.9 |
| Br1—C10 | 1.865 (3) | N4—C12 | 1.256 (3) |
| N1—N2 | 1.355 (3) | N4—C11 | 1.380 (3) |
| N1—C11 | 1.373 (3) | C8—C9 | 1.439 (4) |
| N1—C5 | 1.424 (3) | C9—C10 | 1.394 (4) |
| N2—C9 | 1.330 (3) | C10—C11 | 1.382 (4) |
| N3—C8 | 1.127 (4) | ||
| N2—N1—C11 | 113.7 (2) | C10—C9—C8 | 127.6 (3) |
| N2—N1—C5 | 118.7 (2) | C11—C10—C9 | 105.6 (2) |
| C11—N1—C5 | 127.5 (2) | C11—C10—Br1 | 129.0 (2) |
| C9—N2—N1 | 103.2 (2) | C9—C10—Br1 | 125.4 (2) |
| C12—N4—C11 | 120.3 (2) | N1—C11—N4 | 117.6 (2) |
| N3—C8—C9 | 177.9 (4) | N1—C11—C10 | 104.7 (2) |
| N2—C9—C10 | 112.8 (2) | N4—C11—C10 | 137.6 (2) |
| N2—C9—C8 | 119.5 (2) | N4—C12—C13 | 123.8 (3) |
This work was supported by the Natural Science Foundation of Fujian Province (No. B0610033).
Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Winsonsin, USA.
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.
Zhong, P., Yang, Z. & Shi, Q. (2005). Acta Cryst. E61, o786–o787.
The title compound, (I) (Fig. 1), is similar to the effective insecticides used to treat animals such as cows and sheep (Philippe, 1997, 2000). Earlier we reported on a structure with the same ring system but without the Br substituent on the pyrazole ring (Zhong et al., 2005). That molecule had an overall U shape and exhibited some π-π interactions between the pyrazole and nitro benzene rings. (I) has an overall L shape with the pyrazole ring being essentially coplanar with the nitro benzene ring (dihedral angle of 3.6 (2)°) and approximately perpendicular to the trifluoro phenyl ring (dihedral angle of 88.5 (2)°) and it shows no π-π interactions in the molecular packing. All bond lengths and angles are normal.