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

Li, S.-Y.; Zhong, P.; Hu, M.-L.; Li, J.-H.

doi:10.1107/S1600536806023919

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

S.-Y. Li, P. Zhong, M.-L. Hu and J.-H. Li

In the title compound, C₁₁H₄Cl₃F₃N₄, the dihedral angle between the pyrazole and the N-substituted benzene ring planes is 84.5 (2)°. The crystal structure is stabilized by N—H

N hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806023919/sj2080sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536806023919/sj2080Isup2.hkl Contains datablock I

CCDC reference: 614883

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.009 Å
R factor = 0.069
wR factor = 0.174
Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level A
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 .............       3.70 prolat
PLAT213_ALERT_2_C Atom F2      has ADP max/min Ratio .............       3.20 prolat
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.37
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          9
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C8     -   C11    ...       1.44 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl2    ..  F3      ..       3.12 Ang.
PLAT731_ALERT_1_C Bond    Calc     0.84(7), Rep     0.84(2) ......       3.50 su-Rat
              N4   -H4A     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(6), Rep     0.84(2) ......       3.00 su-Rat
              N4   -H4B     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(7), Rep     0.84(2) ......       3.50 su-Rat
              N4   -H4A     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(6), Rep     0.84(2) ......       3.00 su-Rat
              N4   -H4B     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.25(6), Rep     2.26(2) ......       3.00 su-Rat
              H4B  -N3      1.555   4.554

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.19
           From the CIF: _reflns_number_total               2609
           Count of symmetry unique reflns         1384
           Completeness (_total/calc)            188.51%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1225
           Fraction of Friedel pairs measured     0.885
           Are heavy atom types Z>Si present        yes

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

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

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.

4-Chloro-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-amino-1H-pyrazole- 3-carbonitrile top

Crystal data top

C₁₁H₄Cl₃F₃N₄	D_x = 1.604 Mg m⁻³
M_r = 355.53	Melting point = 452–454 K
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 1391 reflections
a = 11.4138 (9) Å	θ = 2.6–24.2°
b = 9.5508 (8) Å	µ = 0.65 mm⁻¹
c = 13.5082 (11) Å	T = 298 K
V = 1472.5 (2) Å³	Block, colorless
Z = 4	0.24 × 0.10 × 0.09 mm
F(000) = 704

Data collection top

Bruker APEX area-detector diffractometer	2609 independent reflections
Radiation source: fine-focus sealed tube	2169 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
φ and ω scans	θ_max = 25.2°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −13→12
T_min = 0.859, T_max = 0.944	k = −11→10
7390 measured reflections	l = −16→16

Refinement top

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)] = 0.069	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.174	w = 1/[σ²(F_o²) + (0.0912P)² + 0.7048P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2609 reflections	Δρ_max = 0.56 e Å⁻³
196 parameters	Δρ_min = −0.33 e Å⁻³
3 restraints	Absolute structure: Flack (1983), 1226 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.08 (14)

Special details top

Experimental. IR (KBr, ν cm^-1): 3494, 3322, 2260, 1642, 1580, 1509, 1470, 1390, 1319, 879, 820; ¹H NMR (C₃D₆O, δ, p.p.m.): 9.10 (s, 2H), 6.05 (d, J = 10.2 Hz, 2H); ¹³C NMR (C₃D₆O, δ, p.p.m.): 147.3, 145.8, 136.5 (2 C), 134.2 (q, J=34.4 Hz, 1 C), 126.4(2 C), 124.2 (q, J=271.5 Hz, 1 C), 112.3, 111.7, 92.8.

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

	x	y	z	U_iso*/U_eq
Cl1	0.29343 (19)	−0.0380 (2)	0.68923 (17)	0.0894 (7)
Cl2	0.09988 (17)	0.45654 (19)	0.78296 (15)	0.0782 (6)
Cl3	0.42524 (13)	0.23051 (17)	1.05434 (13)	0.0665 (5)
F1	0.0563 (16)	0.1444 (10)	0.3838 (6)	0.258 (8)
F2	−0.0562 (8)	0.2679 (15)	0.4322 (7)	0.251 (7)
F3	0.0835 (7)	0.3568 (9)	0.3915 (5)	0.162 (3)
N1	0.2272 (4)	0.1941 (5)	0.8267 (3)	0.0457 (11)
N2	0.1592 (4)	0.1174 (6)	0.8899 (4)	0.0568 (13)
N3	0.1404 (6)	−0.0067 (10)	1.1277 (6)	0.096 (2)
N4	0.4028 (4)	0.3245 (6)	0.8201 (5)	0.0604 (13)
C1	0.0603 (10)	0.2473 (10)	0.4328 (7)	0.095 (3)
C2	0.1055 (6)	0.2319 (7)	0.5373 (5)	0.0626 (18)
C3	0.1706 (6)	0.1178 (7)	0.5597 (5)	0.0654 (16)
H3	0.1872	0.0497	0.5125	0.078*
C4	0.2119 (5)	0.1066 (7)	0.6574 (5)	0.0573 (16)
C5	0.1886 (4)	0.2113 (6)	0.7266 (4)	0.0449 (13)
C6	0.1256 (5)	0.3248 (6)	0.6978 (5)	0.0528 (14)
C7	0.0804 (6)	0.3362 (8)	0.6042 (6)	0.0641 (18)
H7	0.0341	0.4123	0.5865	0.077*
C8	0.2189 (5)	0.1200 (7)	0.9739 (4)	0.0514 (14)
C9	0.3214 (5)	0.1978 (6)	0.9644 (4)	0.0470 (13)
C10	0.3253 (5)	0.2456 (6)	0.8692 (4)	0.0456 (13)
C11	0.1734 (6)	0.0504 (8)	1.0603 (6)	0.0664 (17)
H4A	0.459 (5)	0.354 (8)	0.855 (5)	0.080*
H4B	0.385 (6)	0.374 (7)	0.770 (4)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1019 (14)	0.0746 (12)	0.0916 (13)	0.0270 (10)	−0.0322 (11)	−0.0049 (11)
Cl2	0.0835 (12)	0.0761 (11)	0.0750 (11)	0.0207 (9)	−0.0045 (9)	−0.0111 (9)
Cl3	0.0662 (9)	0.0787 (10)	0.0545 (8)	−0.0069 (8)	−0.0241 (8)	0.0080 (9)
F1	0.52 (2)	0.139 (6)	0.114 (6)	0.094 (10)	−0.180 (10)	−0.036 (6)
F2	0.159 (8)	0.48 (2)	0.120 (7)	−0.063 (10)	−0.086 (6)	0.081 (10)
F3	0.249 (9)	0.159 (6)	0.080 (4)	−0.067 (6)	−0.055 (5)	0.059 (4)
N1	0.041 (2)	0.057 (3)	0.039 (2)	−0.008 (2)	−0.004 (2)	0.009 (2)
N2	0.047 (2)	0.076 (4)	0.047 (3)	−0.003 (2)	−0.006 (2)	0.019 (3)
N3	0.070 (4)	0.146 (7)	0.072 (4)	−0.003 (4)	0.005 (3)	0.054 (4)
N4	0.043 (2)	0.071 (4)	0.068 (3)	−0.012 (2)	−0.016 (2)	0.018 (3)
C1	0.134 (8)	0.081 (6)	0.069 (6)	−0.025 (5)	−0.045 (5)	0.007 (5)
C2	0.077 (4)	0.056 (4)	0.055 (4)	−0.020 (3)	−0.022 (3)	0.018 (3)
C3	0.082 (4)	0.061 (4)	0.054 (4)	−0.005 (3)	−0.016 (3)	−0.008 (4)
C4	0.057 (3)	0.053 (4)	0.062 (4)	0.004 (3)	−0.013 (3)	0.008 (3)
C5	0.036 (2)	0.051 (3)	0.048 (3)	−0.007 (2)	−0.003 (2)	0.005 (3)
C6	0.041 (3)	0.060 (4)	0.057 (4)	−0.004 (3)	−0.001 (3)	0.000 (3)
C7	0.064 (4)	0.056 (4)	0.072 (4)	−0.005 (3)	−0.018 (3)	0.023 (4)
C8	0.042 (3)	0.071 (4)	0.042 (3)	0.004 (3)	−0.001 (2)	0.009 (3)
C9	0.046 (3)	0.051 (3)	0.043 (3)	0.007 (2)	−0.007 (3)	0.004 (3)
C10	0.042 (3)	0.044 (3)	0.051 (3)	0.001 (2)	0.002 (2)	0.002 (3)
C11	0.056 (3)	0.085 (5)	0.059 (4)	−0.001 (3)	−0.010 (3)	0.015 (4)

Geometric parameters (Å, º) top

Cl1—C4	1.721 (6)	N4—H4B	0.84 (2)
Cl2—C6	1.730 (6)	C1—C2	1.510 (10)
Cl3—C9	1.726 (5)	C2—C3	1.353 (9)
F1—C1	1.186 (11)	C2—C7	1.375 (11)
F2—C1	1.344 (13)	C3—C4	1.405 (9)
F3—C1	1.214 (11)	C3—H3	0.9300
N1—C10	1.351 (7)	C4—C5	1.394 (9)
N1—N2	1.367 (7)	C5—C6	1.358 (8)
N1—C5	1.431 (7)	C6—C7	1.369 (10)
N2—C8	1.323 (7)	C7—H7	0.9300
N3—C11	1.126 (9)	C8—C9	1.392 (8)
N4—C10	1.338 (8)	C8—C11	1.440 (10)
N4—H4A	0.84 (2)	C9—C10	1.365 (8)

C10—N1—N2	113.6 (4)	C3—C4—Cl1	118.5 (5)
C10—N1—C5	128.0 (5)	C6—C5—C4	118.8 (5)
N2—N1—C5	118.5 (4)	C6—C5—N1	121.7 (5)
C8—N2—N1	103.5 (5)	C4—C5—N1	119.5 (5)
C10—N4—H4A	115 (5)	C5—C6—C7	121.9 (6)
C10—N4—H4B	123 (5)	C5—C6—Cl2	118.7 (5)
H4A—N4—H4B	116 (7)	C7—C6—Cl2	119.5 (5)
F1—C1—F3	117.7 (11)	C6—C7—C2	118.1 (6)
F1—C1—F2	94.6 (11)	C6—C7—H7	121.0
F3—C1—F2	95.0 (10)	C2—C7—H7	121.0
F1—C1—C2	117.1 (8)	N2—C8—C9	111.3 (5)
F3—C1—C2	116.0 (8)	N2—C8—C11	120.0 (5)
F2—C1—C2	111.0 (9)	C9—C8—C11	128.6 (5)
C3—C2—C7	123.4 (6)	C10—C9—C8	107.0 (5)
C3—C2—C1	118.3 (7)	C10—C9—Cl3	125.5 (5)
C7—C2—C1	118.3 (7)	C8—C9—Cl3	127.5 (4)
C2—C3—C4	117.1 (6)	N4—C10—N1	122.8 (5)
C2—C3—H3	121.5	N4—C10—C9	132.6 (6)
C4—C3—H3	121.5	N1—C10—C9	104.6 (5)
C5—C4—C3	120.7 (6)	N3—C11—C8	178.1 (8)
C5—C4—Cl1	120.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N2ⁱ	0.84 (2)	2.35 (4)	3.125 (7)	153 (7)
N4—H4B···N3ⁱⁱ	0.84 (2)	2.26 (2)	3.098 (9)	172 (7)

Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) −x+1/2, y+1/2, z−1/2.

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

Supporting information

Key indicators

checkCIF/PLATON results

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