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

The title compound, C₁₈H₈BrCl₂F₃N₄, is a tricyclic imine with an overall Y shape, in which each of the three rings is planar. The pyrazole ring and the adjacent benzene ring make a dihedral angle of 88.1 (2)°. The dihedral angle between the pyrazole ring and the bromo-substituted benzene ring is 160.8 (1)°.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.012 Å
• R factor = 0.072
• wR factor = 0.192
• Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level B
SYMMS02_ALERT_1_B  The unit-cell lengths a and b should not be equal for a
            triclinic cell
            Cell       9.7930    9.7930   11.8650
            Angles    68.3610   68.3610   69.1700

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.97
PLAT146_ALERT_4_C su on gamma    Small or Missing  (x 10000) .....          0 Deg.
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C18
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         12
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C10    -   C11    ...       1.45 Ang.

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   0 ALERT type 5 Informative message, check

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Computing details

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.

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

Crystal data

C18H8BrCl2F3N4	Z = 2
Mr = 488.09	F(000) = 480
Triclinic, P1	Dx = 1.705 Mg m^−3
Hall symbol: -P 1	Melting point = 450–451 K
a = 9.793 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.793 (3) Å	Cell parameters from 967 reflections
c = 11.865 (3) Å	θ = 2.3–24.2°
α = 68.361 (3)°	µ = 2.48 mm^−1
β = 68.361 (3)°	T = 298 K
γ = 69.17°	Block, colorless
V = 950.9 (5) Å^3	0.24 × 0.19 × 0.16 mm

Data collection

Bruker APEX area-detector diffractometer	3372 independent reflections
Radiation source: fine-focus sealed tube	1934 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
φ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→11
Tmin = 0.587, Tmax = 0.692	k = −11→11
4039 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.192	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.088P)^2 + 0.6462P] where P = (Fo^2 + 2Fc^2)/3
3072 reflections	(Δ/σ)max = 0.001
253 parameters	Δρmax = 0.86 e Å^−3
0 restraints	Δρmin = −0.63 e Å^−3

Special details

Experimental. IR (KBr, ν cm^-1): 3441, 2241, 1616, 1502, 1398, 1315, 882, 823; ¹H NMR (CD₃COCD₃, 300 MHz): δ 9.08 (s, 1H), 8.13 (s, 2H), 7.73 (d, J = 1.96 Hz, 2H), 7.69 (d, J = 1.94 Hz, 2H), 7.30 (s, 1H); ¹³C NMR (CD₃COCD₃, 75 MHz): δ 164.9 (N═C), 152.6 (1 C, N pyrazole), 137.0 (1 C), 135.7 (1 C, pyrazole), 134.2 (1 C, pyrazole), 133.8 (q, J = 34.2 Hz, 1 C), 132.3 (2 C), 131.0 (2 C), 127.4 (1 C), 126.2 (2 C), 126.1 (2 C),120.6 (q, J = 271.1 Hz, 1 C), 113.3 (1 C), 98.2 (1 C, pyrazole).

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.30435 (10)	1.29913 (10)	1.08961 (9)	0.0652 (4)
Cl1	0.6177 (3)	0.4332 (3)	0.8134 (2)	0.0769 (8)
Cl2	0.3876 (3)	0.8577 (3)	0.4445 (2)	0.0748 (7)
F1	1.0526 (6)	0.6912 (7)	0.4424 (7)	0.112 (2)
F2	0.9402 (6)	0.8475 (7)	0.5527 (6)	0.0955 (18)
F3	0.9304 (6)	0.9125 (7)	0.3648 (5)	0.0969 (18)
N1	0.3008 (7)	0.7941 (6)	0.8103 (6)	0.0436 (15)
N2	0.3721 (6)	0.6221 (6)	0.6908 (5)	0.0401 (14)
N3	0.3311 (7)	0.5140 (6)	0.6735 (6)	0.0475 (15)
N4	0.0418 (8)	0.3309 (8)	0.7891 (8)	0.071 (2)
C1	0.2834 (8)	1.1485 (8)	1.0361 (7)	0.0435 (18)
C2	0.1803 (8)	1.0633 (8)	1.1158 (7)	0.052 (2)
H2	0.1225	1.0790	1.1942	0.062*
C3	0.1656 (8)	0.9556 (8)	1.0765 (7)	0.050 (2)
H3	0.0975	0.8971	1.1294	0.060*
C4	0.2505 (8)	0.9319 (7)	0.9587 (7)	0.0431 (18)
C5	0.3547 (8)	1.0192 (8)	0.8817 (7)	0.0433 (18)
H5	0.4142	1.0031	0.8037	0.052*
C6	0.3704 (8)	1.1276 (8)	0.9196 (7)	0.0486 (19)
H6	0.4386	1.1862	0.8675	0.058*
C7	0.2302 (8)	0.8195 (8)	0.9178 (8)	0.049 (2)
H7	0.1617	0.7625	0.9732	0.059*
C8	0.2692 (8)	0.6821 (7)	0.7844 (6)	0.0378 (17)
C9	0.1515 (8)	0.6161 (8)	0.8285 (7)	0.0432 (18)
H9	0.0619	0.6350	0.8915	0.052*
C10	0.1964 (8)	0.5139 (8)	0.7576 (7)	0.0432 (18)
C11	0.1131 (8)	0.4096 (8)	0.7722 (8)	0.0482 (19)
C12	0.5177 (7)	0.6530 (7)	0.6247 (7)	0.0369 (17)
C13	0.6386 (8)	0.5784 (7)	0.6756 (7)	0.0451 (18)
C14	0.7731 (8)	0.6224 (8)	0.6221 (8)	0.0501 (19)
H14	0.8540	0.5710	0.6576	0.060*
C15	0.7861 (8)	0.7418 (8)	0.5169 (7)	0.0452 (19)
C16	0.6697 (9)	0.8156 (8)	0.4595 (7)	0.051 (2)
H16	0.6811	0.8949	0.3862	0.062*
C17	0.5355 (8)	0.7694 (8)	0.5131 (7)	0.0445 (18)
C18	0.9269 (10)	0.7984 (10)	0.4700 (9)	0.062 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0730 (6)	0.0549 (5)	0.0767 (7)	−0.0213 (4)	−0.0140 (5)	−0.0295 (5)
Cl1	0.0761 (15)	0.0618 (13)	0.0784 (17)	−0.0309 (12)	−0.0310 (13)	0.0195 (12)
Cl2	0.0627 (14)	0.0776 (15)	0.0728 (16)	−0.0192 (12)	−0.0287 (12)	0.0032 (12)
F1	0.045 (3)	0.099 (4)	0.182 (7)	−0.019 (3)	0.003 (4)	−0.062 (5)
F2	0.091 (4)	0.135 (5)	0.092 (4)	−0.071 (4)	−0.006 (3)	−0.045 (4)
F3	0.084 (4)	0.106 (4)	0.086 (4)	−0.061 (3)	0.002 (3)	−0.002 (4)
N1	0.044 (3)	0.041 (3)	0.046 (4)	−0.010 (3)	−0.002 (3)	−0.023 (3)
N2	0.042 (3)	0.036 (3)	0.043 (4)	−0.015 (3)	−0.004 (3)	−0.013 (3)
N3	0.048 (4)	0.043 (3)	0.056 (4)	−0.017 (3)	−0.007 (3)	−0.021 (3)
N4	0.061 (4)	0.057 (4)	0.107 (6)	−0.025 (4)	−0.020 (4)	−0.028 (4)
C1	0.051 (4)	0.041 (4)	0.041 (5)	−0.009 (3)	−0.011 (4)	−0.017 (3)
C2	0.052 (5)	0.041 (4)	0.053 (5)	−0.012 (4)	0.004 (4)	−0.021 (4)
C3	0.048 (4)	0.045 (4)	0.048 (5)	−0.019 (4)	0.000 (4)	−0.010 (4)
C4	0.043 (4)	0.033 (4)	0.043 (5)	−0.005 (3)	−0.008 (4)	−0.009 (3)
C5	0.039 (4)	0.045 (4)	0.044 (5)	−0.013 (3)	−0.006 (3)	−0.012 (3)
C6	0.050 (5)	0.047 (4)	0.049 (5)	−0.019 (4)	−0.014 (4)	−0.006 (4)
C7	0.049 (5)	0.038 (4)	0.058 (6)	−0.015 (4)	−0.013 (4)	−0.007 (4)
C8	0.037 (4)	0.034 (3)	0.038 (4)	0.001 (3)	−0.012 (3)	−0.013 (3)
C9	0.036 (4)	0.042 (4)	0.053 (5)	−0.011 (3)	−0.008 (4)	−0.018 (4)
C10	0.040 (4)	0.038 (4)	0.054 (5)	−0.012 (3)	−0.019 (4)	−0.007 (4)
C11	0.044 (4)	0.040 (4)	0.061 (5)	−0.007 (4)	−0.015 (4)	−0.017 (4)
C12	0.037 (4)	0.030 (3)	0.046 (5)	−0.007 (3)	−0.007 (3)	−0.018 (3)
C13	0.048 (5)	0.033 (4)	0.048 (5)	−0.007 (3)	−0.010 (4)	−0.009 (3)
C14	0.043 (4)	0.047 (4)	0.058 (5)	−0.005 (4)	−0.010 (4)	−0.021 (4)
C15	0.042 (4)	0.045 (4)	0.045 (5)	−0.013 (4)	−0.001 (4)	−0.018 (4)
C16	0.064 (5)	0.048 (4)	0.039 (5)	−0.026 (4)	−0.010 (4)	0.000 (4)
C17	0.042 (4)	0.042 (4)	0.048 (5)	−0.009 (3)	−0.011 (4)	−0.014 (4)
C18	0.053 (5)	0.071 (6)	0.065 (6)	−0.031 (5)	−0.004 (5)	−0.021 (5)

Geometric parameters (Å, º)

Br1—C1	1.903 (7)	C4—C5	1.402 (9)
Cl1—C13	1.727 (7)	C4—C7	1.452 (10)
Cl2—C17	1.722 (8)	C5—C6	1.368 (10)
F1—C18	1.327 (10)	C5—H5	0.9300
F2—C18	1.303 (10)	C6—H6	0.9300
F3—C18	1.332 (10)	C7—H7	0.9300
N1—C7	1.275 (9)	C8—C9	1.362 (9)
N1—C8	1.398 (8)	C9—C10	1.393 (10)
N2—C8	1.352 (8)	C9—H9	0.9300
N2—N3	1.359 (7)	C10—C11	1.448 (10)
N2—C12	1.431 (8)	C12—C13	1.374 (10)
N3—C10	1.329 (9)	C12—C17	1.393 (10)
N4—C11	1.135 (9)	C13—C14	1.382 (10)
C1—C6	1.376 (10)	C14—C15	1.361 (10)
C1—C2	1.387 (10)	C14—H14	0.9300
C2—C3	1.368 (10)	C15—C16	1.381 (10)
C2—H2	0.9300	C15—C18	1.507 (10)
C3—C4	1.394 (10)	C16—C17	1.390 (10)
C3—H3	0.9300	C16—H16	0.9300
C7—N1—C8	117.3 (6)	C8—C9—H9	128.0
C8—N2—N3	112.9 (5)	C10—C9—H9	128.0
C8—N2—C12	125.1 (6)	N3—C10—C9	113.7 (6)
N3—N2—C12	121.6 (5)	N3—C10—C11	120.3 (7)
C10—N3—N2	102.4 (6)	C9—C10—C11	125.9 (7)
C6—C1—C2	121.9 (7)	N4—C11—C10	176.1 (9)
C6—C1—Br1	119.2 (5)	C13—C12—C17	118.8 (6)
C2—C1—Br1	118.9 (6)	C13—C12—N2	120.7 (6)
C3—C2—C1	118.5 (7)	C17—C12—N2	120.3 (6)
C3—C2—H2	120.7	C12—C13—C14	121.2 (7)
C1—C2—H2	120.7	C12—C13—Cl1	119.0 (5)
C2—C3—C4	121.3 (7)	C14—C13—Cl1	119.7 (6)
C2—C3—H3	119.3	C15—C14—C13	119.4 (7)
C4—C3—H3	119.3	C15—C14—H14	120.3
C3—C4—C5	118.3 (7)	C13—C14—H14	120.3
C3—C4—C7	120.4 (7)	C14—C15—C16	121.2 (7)
C5—C4—C7	121.3 (7)	C14—C15—C18	117.9 (8)
C6—C5—C4	121.0 (7)	C16—C15—C18	120.7 (7)
C6—C5—H5	119.5	C15—C16—C17	119.0 (6)
C4—C5—H5	119.5	C15—C16—H16	120.5
C5—C6—C1	118.9 (7)	C17—C16—H16	120.5
C5—C6—H6	120.5	C16—C17—C12	120.3 (7)
C1—C6—H6	120.5	C16—C17—Cl2	120.6 (6)
N1—C7—C4	123.9 (7)	C12—C17—Cl2	119.1 (6)
N1—C7—H7	118.0	F2—C18—F1	107.3 (8)
C4—C7—H7	118.0	F2—C18—F3	106.4 (7)
N2—C8—C9	106.9 (6)	F1—C18—F3	105.4 (8)
N2—C8—N1	117.5 (6)	F2—C18—C15	112.0 (7)
C9—C8—N1	135.5 (6)	F1—C18—C15	112.2 (7)
C8—C9—C10	104.0 (6)	F3—C18—C15	113.2 (8)