5-(2,4-Dichlorobenzamido)-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carbonitrile
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805027054/hg6237sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805027054/hg6237Isup2.hkl |
CCDC reference: 287593
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.008 Å
- R factor = 0.093
- wR factor = 0.244
- Data-to-parameter ratio = 13.9
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT213_ALERT_2_A Atom F3 has ADP max/min Ratio ............. 6.30 prolat
Author Response: see _publ_section_exptl_refinement |
PLAT242_ALERT_2_A Check Low Ueq as Compared to Neighbors for C1
Author Response: see _publ_section_exptl_refinement |
Alert level C PLAT213_ALERT_2_C Atom F1 has ADP max/min Ratio ............. 3.80 prolat
Author Response: see _publ_section_exptl_refinement |
PLAT213_ALERT_2_C Atom F2 has ADP max/min Ratio ............. 3.60 prolat
Author Response: see _publ_section_exptl_refinement |
PLAT230_ALERT_2_C Hirshfeld Test Diff for F2 - C1 .. 6.37 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C14
Author Response: see _publ_section_exptl_refinement |
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C16
Author Response: see _publ_section_exptl_refinement |
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.08 PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 8 PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C8 - C11 ... 1.44 Ang. PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 41 N2 -C8 -C11 -N3 -143.00 12.00 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 42 C9 -C8 -C11 -N3 33.00 13.00 1.555 1.555 1.555 1.555
2 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 9 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion
Following the method of Hatton et al. (1993), the reaction of 2,6-dichloro-4- trifluoromethylamine with a suspension of nitrosyl sulfuric acid, followed by reaction with a solution of ethyl 2,3-dicyanopropionate in acetic acid, gave 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole, which was then refluxed with 2,4-dichlorobenzoyl chloride and pyridine in chloroform overnight to give the title compound, (I). Please give details of quantities of reagents, reaction conditions etc. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an acetone solution (m.p. 505–506 K). IR (KBr, cm−1): ν 3420, 2252, 1705, 1627,1554, 1380, 1307, 1191, 881; 1H NMR (CDCl3, p.p.m.): δ 10.22 (s,1H), 8.10 (s, 2H), 7.55 (d, 2H), 7.50 (d, 1H), 7.40 (s, 1H); 13C NMR (CDCl3, p.p.m.): δ 163.9 (1 C), 140.7 (1 C), 137.5 (1 C), 137.4 (1 C), 136.7 (1 C), 135.3 (1 C), 134.8 (1 C), 134.7 (1 C), 132.7 (1 C), 131.4 (1 C), 130.4 (1 C), 128.4 (1 C), 128.3 (1 C), 127.5 (1 C), 127.4 (2 C), 127.3 (1 C), 125.1 (1 C).
The H atoms were positioned geometrically and allowed to ride on their parent atoms at distances of C—H = 0.93 Å and N—H = 0.86 Å with Uiso(H) = 1.2Ueq(parent atom). 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 disorder model were unsuccessful. The inability to account for the electron-density distribution in the vicinity of the CF3 group is the most likely reason for the limited overall precision of the structure and the high R value.
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97.
Fig. 1. The structure of (I), showing the atom-numbering scheme and with displacement ellipsoids for non-H atoms at the 50% probability level. |
C18H7Cl4F3N4O | F(000) = 984 |
Mr = 494.08 | Dx = 1.564 Mg m−3 |
Monoclinic, P21/n | Melting point: 505 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7760 (11) Å | Cell parameters from 1812 reflections |
b = 16.4530 (16) Å | θ = 2.8–24.3° |
c = 16.6220 (16) Å | µ = 0.61 mm−1 |
β = 99.31 (3)° | T = 298 K |
V = 2098.6 (5) Å3 | Block, colorless |
Z = 4 | 0.35 × 0.27 × 0.17 mm |
Bruker APEX area-detector diffractometer | 3779 independent reflections |
Radiation source: fine-focus sealed tube | 3196 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ϕ and ω scans | θmax = 25.2°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −9→8 |
Tmin = 0.815, Tmax = 0.904 | k = −17→19 |
10608 measured reflections | l = −18→19 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.093 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.244 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.1073P)2 + 5.2953P] where P = (Fo2 + 2Fc2)/3 |
3779 reflections | (Δ/σ)max < 0.001 |
271 parameters | Δρmax = 1.02 e Å−3 |
0 restraints | Δρmin = −0.69 e Å−3 |
C18H7Cl4F3N4O | V = 2098.6 (5) Å3 |
Mr = 494.08 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.7760 (11) Å | µ = 0.61 mm−1 |
b = 16.4530 (16) Å | T = 298 K |
c = 16.6220 (16) Å | 0.35 × 0.27 × 0.17 mm |
β = 99.31 (3)° |
Bruker APEX area-detector diffractometer | 3779 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 3196 reflections with I > 2σ(I) |
Tmin = 0.815, Tmax = 0.904 | Rint = 0.023 |
10608 measured reflections |
R[F2 > 2σ(F2)] = 0.093 | 0 restraints |
wR(F2) = 0.244 | H-atom parameters constrained |
S = 1.07 | Δρmax = 1.02 e Å−3 |
3779 reflections | Δρmin = −0.69 e Å−3 |
271 parameters |
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 | ||
Cl1 | 0.85543 (18) | 0.91195 (11) | 0.22140 (10) | 0.0767 (5) | |
Cl2 | 0.3192 (2) | 0.72751 (11) | 0.27660 (11) | 0.0820 (5) | |
Cl3 | 0.9410 (4) | 0.73550 (16) | 0.05278 (14) | 0.1392 (12) | |
Cl4 | 0.7241 (3) | 0.49917 (13) | −0.15813 (9) | 0.0939 (7) | |
O1 | 0.9513 (6) | 0.5777 (3) | 0.2392 (2) | 0.0816 (14) | |
F1 | 0.0914 (11) | 0.9348 (5) | 0.0479 (6) | 0.237 (5) | |
F2 | 0.1704 (16) | 1.0236 (5) | 0.1032 (6) | 0.261 (6) | |
F3 | 0.2869 (10) | 0.9906 (9) | 0.0181 (6) | 0.335 (9) | |
N1 | 0.6910 (5) | 0.7792 (2) | 0.3001 (2) | 0.0449 (9) | |
N2 | 0.7298 (6) | 0.8052 (3) | 0.3781 (2) | 0.0504 (10) | |
N3 | 0.9928 (7) | 0.7688 (3) | 0.5611 (3) | 0.0726 (15) | |
N4 | 0.7663 (6) | 0.6815 (3) | 0.2071 (2) | 0.0544 (11) | |
H4 | 0.6938 | 0.7041 | 0.1691 | 0.065* | |
C1 | 0.2354 (10) | 0.9653 (5) | 0.0729 (5) | 0.085 (2) | |
C2 | 0.3539 (7) | 0.9168 (3) | 0.1324 (3) | 0.0535 (13) | |
C3 | 0.2871 (6) | 0.8542 (3) | 0.1729 (3) | 0.0527 (13) | |
H3 | 0.1683 | 0.8429 | 0.1631 | 0.063* | |
C4 | 0.3983 (6) | 0.8088 (3) | 0.2280 (3) | 0.0469 (11) | |
C5 | 0.5741 (6) | 0.8257 (3) | 0.2430 (2) | 0.0393 (10) | |
C6 | 0.6372 (6) | 0.8890 (3) | 0.2017 (3) | 0.0454 (11) | |
C7 | 0.5268 (7) | 0.9348 (3) | 0.1460 (3) | 0.0516 (12) | |
H7 | 0.5700 | 0.9772 | 0.1182 | 0.062* | |
C8 | 0.8497 (6) | 0.7522 (3) | 0.4112 (3) | 0.0454 (11) | |
C9 | 0.8913 (7) | 0.6949 (3) | 0.3565 (3) | 0.0517 (12) | |
H9 | 0.9725 | 0.6531 | 0.3661 | 0.062* | |
C10 | 0.7853 (6) | 0.7139 (3) | 0.2845 (3) | 0.0436 (11) | |
C11 | 0.9263 (7) | 0.7620 (3) | 0.4954 (3) | 0.0549 (13) | |
C12 | 0.8574 (7) | 0.6152 (3) | 0.1881 (3) | 0.0531 (12) | |
C13 | 0.8246 (7) | 0.5903 (3) | 0.1004 (3) | 0.0507 (12) | |
C14 | 0.8574 (8) | 0.6381 (4) | 0.0366 (3) | 0.0651 (15) | |
C15 | 0.8280 (9) | 0.6100 (4) | −0.0433 (3) | 0.0728 (17) | |
H15 | 0.8531 | 0.6426 | −0.0856 | 0.087* | |
C16 | 0.7623 (7) | 0.5346 (4) | −0.0585 (3) | 0.0573 (14) | |
C17 | 0.7324 (10) | 0.4848 (4) | 0.0033 (4) | 0.0770 (18) | |
H17 | 0.6906 | 0.4323 | −0.0076 | 0.092* | |
C18 | 0.7651 (10) | 0.5136 (3) | 0.0823 (3) | 0.0734 (18) | |
H18 | 0.7458 | 0.4794 | 0.1245 | 0.088* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0423 (7) | 0.1033 (13) | 0.0825 (11) | −0.0104 (7) | 0.0046 (7) | 0.0070 (9) |
Cl2 | 0.0810 (11) | 0.0840 (11) | 0.0812 (11) | −0.0192 (8) | 0.0142 (8) | 0.0197 (9) |
Cl3 | 0.215 (3) | 0.1225 (18) | 0.0915 (15) | −0.102 (2) | 0.0596 (17) | −0.0308 (13) |
Cl4 | 0.1062 (14) | 0.1224 (16) | 0.0481 (9) | 0.0302 (11) | −0.0022 (8) | −0.0317 (9) |
O1 | 0.110 (3) | 0.086 (3) | 0.044 (2) | 0.052 (3) | −0.003 (2) | 0.001 (2) |
F1 | 0.172 (6) | 0.208 (8) | 0.267 (10) | −0.032 (6) | −0.153 (7) | 0.126 (7) |
F2 | 0.332 (12) | 0.166 (7) | 0.226 (9) | 0.162 (8) | −0.128 (9) | −0.013 (7) |
F3 | 0.158 (6) | 0.65 (2) | 0.216 (8) | 0.207 (10) | 0.090 (6) | 0.340 (13) |
N1 | 0.050 (2) | 0.054 (2) | 0.0269 (18) | 0.0114 (18) | −0.0046 (16) | −0.0026 (16) |
N2 | 0.062 (3) | 0.061 (3) | 0.0250 (18) | 0.007 (2) | −0.0003 (17) | −0.0046 (17) |
N3 | 0.092 (4) | 0.086 (4) | 0.031 (2) | −0.014 (3) | −0.016 (2) | 0.011 (2) |
N4 | 0.066 (3) | 0.061 (3) | 0.032 (2) | 0.023 (2) | −0.0080 (18) | −0.0019 (18) |
C1 | 0.082 (5) | 0.091 (5) | 0.069 (4) | 0.032 (4) | −0.024 (4) | 0.020 (4) |
C2 | 0.057 (3) | 0.060 (3) | 0.040 (3) | 0.014 (2) | −0.003 (2) | 0.000 (2) |
C3 | 0.036 (2) | 0.074 (3) | 0.045 (3) | 0.005 (2) | −0.004 (2) | −0.004 (2) |
C4 | 0.051 (3) | 0.051 (3) | 0.038 (2) | 0.002 (2) | 0.005 (2) | −0.003 (2) |
C5 | 0.043 (2) | 0.047 (2) | 0.026 (2) | 0.008 (2) | −0.0006 (17) | −0.0060 (18) |
C6 | 0.040 (2) | 0.056 (3) | 0.039 (2) | 0.002 (2) | 0.0005 (19) | −0.003 (2) |
C7 | 0.058 (3) | 0.057 (3) | 0.039 (3) | 0.004 (2) | 0.005 (2) | 0.007 (2) |
C8 | 0.054 (3) | 0.051 (3) | 0.027 (2) | 0.000 (2) | −0.0066 (19) | 0.0018 (19) |
C9 | 0.057 (3) | 0.053 (3) | 0.040 (3) | 0.013 (2) | −0.008 (2) | 0.003 (2) |
C10 | 0.051 (3) | 0.048 (3) | 0.030 (2) | 0.006 (2) | −0.0007 (19) | −0.0022 (19) |
C11 | 0.070 (3) | 0.054 (3) | 0.037 (3) | −0.007 (3) | −0.002 (2) | 0.004 (2) |
C12 | 0.061 (3) | 0.058 (3) | 0.039 (3) | 0.015 (3) | 0.002 (2) | −0.003 (2) |
C13 | 0.054 (3) | 0.055 (3) | 0.042 (3) | 0.015 (2) | 0.006 (2) | −0.003 (2) |
C14 | 0.072 (4) | 0.073 (4) | 0.052 (3) | −0.016 (3) | 0.018 (3) | −0.008 (3) |
C15 | 0.085 (4) | 0.091 (5) | 0.046 (3) | −0.011 (4) | 0.022 (3) | −0.002 (3) |
C16 | 0.054 (3) | 0.074 (4) | 0.042 (3) | 0.019 (3) | 0.003 (2) | −0.016 (3) |
C17 | 0.115 (5) | 0.055 (3) | 0.059 (4) | 0.008 (3) | 0.008 (3) | −0.013 (3) |
C18 | 0.124 (6) | 0.050 (3) | 0.046 (3) | 0.011 (3) | 0.013 (3) | 0.002 (2) |
Cl1—C6 | 1.718 (5) | C3—H3 | 0.9300 |
Cl2—C4 | 1.726 (5) | C4—C5 | 1.378 (7) |
Cl3—C14 | 1.733 (6) | C5—C6 | 1.381 (7) |
Cl4—C16 | 1.735 (5) | C6—C7 | 1.380 (7) |
O1—C12 | 1.197 (6) | C7—H7 | 0.9300 |
F1—C1 | 1.235 (10) | C8—C9 | 1.385 (7) |
F2—C1 | 1.230 (11) | C8—C11 | 1.439 (6) |
F3—C1 | 1.132 (9) | C9—C10 | 1.375 (6) |
N1—C10 | 1.349 (6) | C9—H9 | 0.9300 |
N1—N2 | 1.352 (5) | C12—C13 | 1.496 (7) |
N1—C5 | 1.425 (5) | C13—C18 | 1.361 (8) |
N2—C8 | 1.330 (6) | C13—C14 | 1.377 (8) |
N3—C11 | 1.135 (6) | C14—C15 | 1.390 (8) |
N4—C12 | 1.366 (6) | C15—C16 | 1.350 (9) |
N4—C10 | 1.377 (6) | C15—H15 | 0.9300 |
N4—H4 | 0.8600 | C16—C17 | 1.363 (9) |
C1—C2 | 1.473 (7) | C17—C18 | 1.380 (8) |
C2—C7 | 1.359 (7) | C17—H17 | 0.9300 |
C2—C3 | 1.377 (8) | C18—H18 | 0.9300 |
C3—C4 | 1.375 (7) | ||
C10—N1—N2 | 113.1 (4) | N2—C8—C9 | 113.4 (4) |
C10—N1—C5 | 127.4 (4) | N2—C8—C11 | 118.8 (4) |
N2—N1—C5 | 119.2 (4) | C9—C8—C11 | 127.8 (5) |
C8—N2—N1 | 102.9 (4) | C10—C9—C8 | 104.2 (4) |
C12—N4—C10 | 122.9 (4) | C10—C9—H9 | 127.9 |
C12—N4—H4 | 118.5 | C8—C9—H9 | 127.9 |
C10—N4—H4 | 118.5 | N1—C10—C9 | 106.4 (4) |
F3—C1—F2 | 105.4 (11) | N1—C10—N4 | 120.5 (4) |
F3—C1—F1 | 107.4 (9) | C9—C10—N4 | 133.1 (4) |
F2—C1—F1 | 92.5 (9) | N3—C11—C8 | 177.3 (7) |
F3—C1—C2 | 118.4 (7) | O1—C12—N4 | 121.8 (5) |
F2—C1—C2 | 113.7 (7) | O1—C12—C13 | 122.6 (5) |
F1—C1—C2 | 116.1 (7) | N4—C12—C13 | 115.5 (4) |
C7—C2—C3 | 121.6 (5) | C18—C13—C14 | 117.3 (5) |
C7—C2—C1 | 119.2 (6) | C18—C13—C12 | 117.8 (5) |
C3—C2—C1 | 119.2 (6) | C14—C13—C12 | 124.8 (5) |
C4—C3—C2 | 119.1 (5) | C13—C14—C15 | 121.5 (6) |
C4—C3—H3 | 120.5 | C13—C14—Cl3 | 121.4 (4) |
C2—C3—H3 | 120.5 | C15—C14—Cl3 | 117.1 (5) |
C3—C4—C5 | 120.7 (5) | C16—C15—C14 | 119.0 (6) |
C3—C4—Cl2 | 120.0 (4) | C16—C15—H15 | 120.5 |
C5—C4—Cl2 | 119.3 (4) | C14—C15—H15 | 120.5 |
C4—C5—C6 | 118.9 (4) | C15—C16—C17 | 121.1 (5) |
C4—C5—N1 | 121.3 (4) | C15—C16—Cl4 | 119.3 (5) |
C6—C5—N1 | 119.7 (4) | C17—C16—Cl4 | 119.6 (5) |
C7—C6—C5 | 120.9 (4) | C16—C17—C18 | 118.9 (6) |
C7—C6—Cl1 | 119.7 (4) | C16—C17—H17 | 120.6 |
C5—C6—Cl1 | 119.4 (3) | C18—C17—H17 | 120.6 |
C2—C7—C6 | 118.9 (5) | C13—C18—C17 | 122.2 (6) |
C2—C7—H7 | 120.5 | C13—C18—H18 | 118.9 |
C6—C7—H7 | 120.5 | C17—C18—H18 | 118.9 |
C10—N1—N2—C8 | −1.4 (5) | C11—C8—C9—C10 | −177.8 (5) |
C5—N1—N2—C8 | −175.3 (4) | N2—N1—C10—C9 | 0.7 (6) |
F3—C1—C2—C7 | 32.5 (15) | C5—N1—C10—C9 | 174.0 (5) |
F2—C1—C2—C7 | −92.0 (11) | N2—N1—C10—N4 | −177.7 (4) |
F1—C1—C2—C7 | 162.4 (9) | C5—N1—C10—N4 | −4.4 (8) |
F3—C1—C2—C3 | −147.4 (12) | C8—C9—C10—N1 | 0.3 (6) |
F2—C1—C2—C3 | 88.2 (11) | C8—C9—C10—N4 | 178.4 (5) |
F1—C1—C2—C3 | −17.4 (12) | C12—N4—C10—N1 | −179.5 (5) |
C7—C2—C3—C4 | −0.3 (8) | C12—N4—C10—C9 | 2.6 (9) |
C1—C2—C3—C4 | 179.6 (6) | N2—C8—C11—N3 | −143 (12) |
C2—C3—C4—C5 | 0.4 (7) | C9—C8—C11—N3 | 33 (13) |
C2—C3—C4—Cl2 | −177.5 (4) | C10—N4—C12—O1 | 5.1 (9) |
C3—C4—C5—C6 | −0.2 (7) | C10—N4—C12—C13 | −177.9 (5) |
Cl2—C4—C5—C6 | 177.7 (3) | O1—C12—C13—C18 | 55.2 (8) |
C3—C4—C5—N1 | 179.9 (4) | N4—C12—C13—C18 | −121.8 (6) |
Cl2—C4—C5—N1 | −2.2 (6) | O1—C12—C13—C14 | −121.8 (7) |
C10—N1—C5—C4 | 93.6 (6) | N4—C12—C13—C14 | 61.2 (7) |
N2—N1—C5—C4 | −93.5 (5) | C18—C13—C14—C15 | 1.2 (9) |
C10—N1—C5—C6 | −86.3 (6) | C12—C13—C14—C15 | 178.2 (6) |
N2—N1—C5—C6 | 86.6 (5) | C18—C13—C14—Cl3 | −177.6 (5) |
C4—C5—C6—C7 | −0.1 (7) | C12—C13—C14—Cl3 | −0.6 (8) |
N1—C5—C6—C7 | 179.8 (4) | C13—C14—C15—C16 | 1.4 (10) |
C4—C5—C6—Cl1 | 178.7 (4) | Cl3—C14—C15—C16 | −179.7 (5) |
N1—C5—C6—Cl1 | −1.4 (6) | C14—C15—C16—C17 | −3.0 (10) |
C3—C2—C7—C6 | 0.0 (8) | C14—C15—C16—Cl4 | 179.7 (5) |
C1—C2—C7—C6 | −179.8 (5) | C15—C16—C17—C18 | 2.0 (10) |
C5—C6—C7—C2 | 0.2 (7) | Cl4—C16—C17—C18 | 179.3 (5) |
Cl1—C6—C7—C2 | −178.6 (4) | C14—C13—C18—C17 | −2.2 (10) |
N1—N2—C8—C9 | 1.6 (6) | C12—C13—C18—C17 | −179.5 (6) |
N1—N2—C8—C11 | 178.5 (4) | C16—C17—C18—C13 | 0.7 (11) |
N2—C8—C9—C10 | −1.2 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N3i | 0.86 | 2.23 | 3.068 (6) | 166 |
Symmetry code: (i) x−1/2, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C18H7Cl4F3N4O |
Mr | 494.08 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 7.7760 (11), 16.4530 (16), 16.6220 (16) |
β (°) | 99.31 (3) |
V (Å3) | 2098.6 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.61 |
Crystal size (mm) | 0.35 × 0.27 × 0.17 |
Data collection | |
Diffractometer | Bruker APEX area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.815, 0.904 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10608, 3779, 3196 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.093, 0.244, 1.07 |
No. of reflections | 3779 |
No. of parameters | 271 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.02, −0.69 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXL97.
O1—C12 | 1.197 (6) | N4—C10 | 1.377 (6) |
F1—C1 | 1.235 (10) | C1—C2 | 1.473 (7) |
N1—C10 | 1.349 (6) | C5—C6 | 1.381 (7) |
N1—N2 | 1.352 (5) | C8—C9 | 1.385 (7) |
N1—C5 | 1.425 (5) | C13—C18 | 1.361 (8) |
N2—C8 | 1.330 (6) | C13—C14 | 1.377 (8) |
N4—C12 | 1.366 (6) | ||
C10—N1—N2 | 113.1 (4) | N2—C8—C9 | 113.4 (4) |
C10—N1—C5 | 127.4 (4) | C10—C9—C8 | 104.2 (4) |
N2—N1—C5 | 119.2 (4) | N1—C10—N4 | 120.5 (4) |
C8—N2—N1 | 102.9 (4) | C9—C10—N4 | 133.1 (4) |
F3—C1—F2 | 105.4 (11) | O1—C12—N4 | 121.8 (5) |
C7—C2—C3 | 121.6 (5) | N4—C12—C13 | 115.5 (4) |
C7—C2—C1 | 119.2 (6) | C18—C13—C14 | 117.3 (5) |
C3—C4—C5 | 120.7 (5) | C15—C14—Cl3 | 117.1 (5) |
C6—C5—N1 | 119.7 (4) | C16—C17—C18 | 118.9 (6) |
C2—C7—C6 | 118.9 (5) | C13—C18—C17 | 122.2 (6) |
C10—N1—N2—C8 | −1.4 (5) | N1—C5—C6—C7 | 179.8 (4) |
C5—N1—N2—C8 | −175.3 (4) | C3—C2—C7—C6 | 0.0 (8) |
F1—C1—C2—C7 | 162.4 (9) | N2—N1—C10—N4 | −177.7 (4) |
C7—C2—C3—C4 | −0.3 (8) | C12—N4—C10—N1 | −179.5 (5) |
C3—C4—C5—N1 | 179.9 (4) | N4—C12—C13—C14 | 61.2 (7) |
N2—N1—C5—C4 | −93.5 (5) | Cl3—C14—C15—C16 | −179.7 (5) |
C10—N1—C5—C6 | −86.3 (6) | C16—C17—C18—C13 | 0.7 (11) |
N2—N1—C5—C6 | 86.6 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N3i | 0.86 | 2.23 | 3.068 (6) | 166 |
Symmetry code: (i) x−1/2, −y+3/2, z−1/2. |
The title compound, (I), is an intermediate for the synthesis of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethyl-thiopyrazole, 5-amino-3-cyano-1-(2,6-dichloro-4- trifluoromethylphenyl)-4-trifluoromethylsulphenylpyrazole and 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4- trifluoromethylsulfonyl pyrazole, which are all good insecticides (Hatton et al., 1993). The structure of (I) is shown in Fig. 1. The molecule contains three planar groups, forming an overall U shape. All bond lengths and angles are in agreement with those observed in similar compounds (Zhang et al., 2005; Zhong et al., 2005) The dihedral angles between the pyrazole and the C2–C7 and C13–C18 benzene rings are 90.1 (1) and 112.8 (1)°, respectively.