1-(5-Hydroxy-1-phenyl-3-trifluoromethyl-1H-pyrazol-1-yl)ethanone

Gallardo, H.; Girotto, E.; Bortoluzzi, A.J.

doi:10.1107/S1600536809051745

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 1| January 2010| Pages o75-o76

doi:10.1107/S1600536809051745

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1-(5-Hydroxy-1-phenyl-3-trifluoromethyl-1H-pyrazol-1-yl)ethanone

Hugo Gallardo,^a Edivandro Girotto ^a and Adailton J. Bortoluzzi ^a ^*

^aDepto. de Química - Universidade Federal de Santa Catarina, 88040-900 - Florianópolis, SC, Brazil
^*Correspondence e-mail: adajb@qmc.ufsc.br

(Received 2 November 2009; accepted 1 December 2009; online 9 December 2009)

The crystal structure of the title compound, C₁₂H₉F₃N₂O₂, contains two independent molecules in the asymmetric unit. The molecules are chemically identical but exhibit a significant difference in the dihedral angles between the mean planes of the phenyl and pyrazole rings, with values of of 11.62 (13) and 18.17 (11)°. Moreover, the trifluoromethyl group in one of the molecules shows rotational disorder of the F atoms, with site occupancy factors of 0.929 (6) and 0.071 (6). The hydroxyl group in each of the molecules shows a strong intramolecular hydrogen bond with the carbonyl O atom, forming a six-membered ring and forcing the formyl group and pyrazole ring to be coplanarshowing C—C—C—O torsion angles of ?0.3(5)o and 0.°. Weak intermolecular C—H⋯O and C—H⋯F interactions contribute to the stabilization of the crystal packing.

Related literature

For the pharmaceutical activity of pyrazole derivatives, see: Belmar et al. (2001 ). For related structures, see: Gallardo et al. (2009 ); Belmar et al. (2006a ,b ); Pérez et al. (2005 ). For the melting point, see: Bieringer & Holzer (2006 ).

Experimental

Crystal data

C₁₂H₉F₃N₂O₂
M_r = 270.21
Triclinic, $[P \overline 1]$
a = 7.4779 (19) Å
b = 11.9390 (18) Å
c = 13.8587 (14) Å
α = 78.591 (11)°
β = 80.090 (17)°
γ = 78.791 (18)°
V = 1178.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 293 K
0.40 × 0.33 × 0.13 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
4766 measured reflections
4567 independent reflections
2268 reflections with I > 2σ(I)
R_int = 0.025
3 standard reflections every 200 reflections
intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.165
S = 1.04
4567 reflections
373 parameters
81 restraints
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O13	1.18	1.60	2.548 (3)	132
O5′—H5′⋯O13′	1.07	1.65	2.560 (4)	139
C14—H14B⋯F1′ⁱ	0.96	2.55	3.394 (5)	146
C7—H7⋯O13ⁱⁱ	0.93	2.64	3.446 (4)	145
C7′—H7′⋯O13′ⁱⁱⁱ	0.93	2.57	3.406 (4)	149
Symmetry codes: (i) x-1, y+1, z; (ii) -x+1, -y+1, -z+2; (iii) -x+2, -y+1, -z+1.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: HELENA (Spek, 1996 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809051745/pv2233sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051745/pv2233Isup2.hkl

checkCIF report

Comment top

The pyrazolones are derivatives of pyrazole having an additional carbonyl/hydroxy group. Some derivatives of pyrazolone show analgesic and anti-inflamatory properties (Belmar et al., 2001). In this article, the crystal structure of the title compound (I), which is a derivative of pyrazole is presented.

The asymmetric unit of the title compound contains two independent molecules (Fig. 1). The molecules are chemically identical, but show different spacial conformation. This can be evidenced by the different dihedral angle between the mean plane of the phenyl and pyrazole rings of 11.62 (13)° and 18.17 (11)°. In the pyrazole rings of the two molecules the single bond distances are shorter and the double bond distances are longer that expected values indicating that the pyrazole rings are delocalized π-systems. A cyclic six-membered intramolecular hydrogen bond between hydroxyl and acyl groups force the acyl groups and the pyrazole rings to be coplanar, in both molecules. Several weak intermolecular C—H···O and C—H···F hydrogen bonds are involved in the stabilization of the crystal packing. The crystal structures of a few compounds closely related to (I) have been reported (Gallardo et al., 2009; Belmar et al., 2006a,b); Pérez et al., 2005).

Related literature top

For the pharmaceutical activity of pyrazole derivatives, see: Belmar et al. (2001). For related structures, see: Gallardo et al. (2009); Belmar et al. (2006a, 2006b); Pérez et al. (2005). For the melting point, see: Bieringer & Holzer (2006).

Experimental top

In a three necked flask of 50 ml equipped with condenser, were transferred 2-phenyl-5-(trifluoromethyl)pyrazol-3(2H)-one (1.5 g, 6.57 mmol), 1,4-dioxane (dried) (25 ml) and Ca(OH)₂ (0.67 g, 13.1 mmol). The reaction mixture was heated to 373 K with stirring for 15 min, then cooled to room temperature and added slowly ac. acetyl chloride (0.56 g, 7.2 mmol) and allowed to reflux for 24 h. After the reaction was completed, the product was poured into 40 ml of HCl solution (3 mol l^-1) and ice and stirred for 30 min, resulting in precipitate which was filtered. The compound was purified through a silica gel chromatographic column (eluent: hexane/AcOEt 3%) which yielded a yellow solid (0.525 g) of the title compound. In the purification process, 0.752 g of 2-phenyl-5-(trifluoromethyl)pyrazol-3(2H)-one was also recovered.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: HELENA (Spek, 1996); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the two molecules of the title compound with labeling scheme; displacement ellipsoids are shown at the 40% probability level and atoms F1", F2" and F3" representing the smaller fraction of the disordered trifluoromethyl group have been excluded.

1-(5-Hydroxy-1-phenyl-3-trifluoromethyl-1H-pyrazol-1-yl)ethanone top

Crystal data top

C₁₂H₉F₃N₂O₂	Z = 4
M_r = 270.21	F(000) = 552
Triclinic, P1	D_x = 1.523 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 7.4779 (19) Å	Cell parameters from 25 reflections
b = 11.9390 (18) Å	θ = 5.4–18.6°
c = 13.8587 (14) Å	µ = 0.14 mm⁻¹
α = 78.591 (11)°	T = 293 K
β = 80.090 (17)°	Prismatic, yellow
γ = 78.791 (18)°	0.40 × 0.33 × 0.13 mm
V = 1178.2 (4) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.025
Radiation source: fine-focus sealed tube	θ_max = 26.0°, θ_min = 1.5°
Graphite monochromator	h = −9→9
ω/2θ scans	k = −14→14
4766 measured reflections	l = −17→0
4567 independent reflections	3 standard reflections every 200 reflections
2268 reflections with I > 2σ(I)	intensity decay: 1%

Refinement top

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.165	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0571P)² + 0.4943P] where P = (F_o² + 2F_c²)/3
4567 reflections	(Δ/σ)_max = 0.001
373 parameters	Δρ_max = 0.20 e Å⁻³
81 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₂H₉F₃N₂O₂	γ = 78.791 (18)°
M_r = 270.21	V = 1178.2 (4) Å³
Triclinic, P1	Z = 4
a = 7.4779 (19) Å	Mo Kα radiation
b = 11.9390 (18) Å	µ = 0.14 mm⁻¹
c = 13.8587 (14) Å	T = 293 K
α = 78.591 (11)°	0.40 × 0.33 × 0.13 mm
β = 80.090 (17)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.025
4766 measured reflections	3 standard reflections every 200 reflections
4567 independent reflections	intensity decay: 1%
2268 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.055	81 restraints
wR(F²) = 0.165	H-atom parameters constrained
S = 1.04	Δρ_max = 0.20 e Å⁻³
4567 reflections	Δρ_min = −0.21 e Å⁻³
373 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
N1	0.4429 (3)	0.5800 (2)	0.73982 (18)	0.0517 (7)
N2	0.4653 (4)	0.6690 (2)	0.66084 (18)	0.0585 (7)
C3	0.4755 (5)	0.7585 (3)	0.7002 (2)	0.0557 (8)
C4	0.4619 (4)	0.7333 (3)	0.8049 (2)	0.0524 (8)
C5	0.4399 (4)	0.6175 (3)	0.8262 (2)	0.0536 (8)
O5	0.4173 (3)	0.55236 (19)	0.91394 (16)	0.0695 (7)
H5	0.4804	0.6027	0.9610	0.083*
C6	0.4214 (4)	0.4699 (3)	0.7213 (2)	0.0508 (8)
C7	0.4301 (5)	0.3738 (3)	0.7950 (3)	0.0668 (10)
H7	0.4494	0.3792	0.8583	0.080*
C8	0.4099 (5)	0.2695 (3)	0.7735 (3)	0.0749 (11)
H8	0.4140	0.2046	0.8233	0.090*
C9	0.3840 (5)	0.2594 (3)	0.6807 (3)	0.0738 (11)
H9	0.3725	0.1881	0.6670	0.089*
C10	0.3752 (5)	0.3559 (3)	0.6079 (3)	0.0718 (10)
H10	0.3567	0.3499	0.5446	0.086*
C11	0.3934 (5)	0.4620 (3)	0.6275 (2)	0.0633 (9)
H11	0.3869	0.5271	0.5779	0.076*
C12	0.4960 (7)	0.8687 (3)	0.6304 (3)	0.0751 (11)
F1	0.5010 (8)	0.8597 (3)	0.5363 (2)	0.1229 (17)	0.929 (6)
F1''	0.362 (5)	0.899 (4)	0.585 (3)	0.119 (13)	0.071 (6)
F2	0.3541 (5)	0.9518 (2)	0.6488 (3)	0.1112 (14)	0.929 (6)
F2''	0.508 (7)	0.955 (3)	0.667 (3)	0.106 (11)	0.071 (6)
F3	0.6442 (6)	0.9097 (3)	0.6361 (3)	0.1119 (14)	0.929 (6)
F3''	0.637 (6)	0.850 (3)	0.573 (3)	0.096 (12)	0.071 (6)
C13	0.4653 (5)	0.7924 (3)	0.8855 (3)	0.0643 (9)
O13	0.4473 (4)	0.7366 (2)	0.97198 (18)	0.0839 (8)
C14	0.4909 (6)	0.9153 (3)	0.8704 (3)	0.0849 (12)
H14A	0.4708	0.9407	0.9335	0.127*
H14B	0.4046	0.9625	0.8290	0.127*
H14C	0.6140	0.9221	0.8388	0.127*
N1'	0.9141 (4)	0.4419 (2)	0.7688 (2)	0.0561 (7)
N2'	0.9250 (4)	0.3460 (2)	0.8425 (2)	0.0612 (7)
C3'	0.9172 (4)	0.2592 (3)	0.7996 (3)	0.0587 (9)
C4'	0.9010 (4)	0.2929 (3)	0.6972 (2)	0.0578 (9)
C5'	0.8996 (4)	0.4117 (3)	0.6816 (2)	0.0569 (8)
O5'	0.8858 (3)	0.4856 (2)	0.59906 (17)	0.0747 (7)
H5'	0.8542	0.4376	0.5487	0.090*
C6'	0.9283 (4)	0.5517 (3)	0.7911 (2)	0.0536 (8)
C7'	0.9738 (5)	0.6410 (3)	0.7169 (3)	0.0655 (9)
H7'	0.9917	0.6317	0.6506	0.079*
C8'	0.9925 (5)	0.7435 (3)	0.7409 (3)	0.0737 (11)
H8'	1.0230	0.8038	0.6908	0.088*
C9'	0.9668 (5)	0.7580 (3)	0.8383 (3)	0.0778 (11)
H9'	0.9813	0.8276	0.8542	0.093*
C10'	0.9198 (5)	0.6702 (3)	0.9119 (3)	0.0768 (11)
H10'	0.9013	0.6805	0.9779	0.092*
C11'	0.8993 (5)	0.5662 (3)	0.8896 (3)	0.0652 (9)
H11'	0.8666	0.5067	0.9399	0.078*
C12'	0.9344 (6)	0.1406 (3)	0.8617 (3)	0.0736 (10)
F1'	1.0741 (4)	0.06809 (19)	0.8220 (2)	0.1054 (8)
F2'	0.9629 (4)	0.14090 (19)	0.95283 (18)	0.1084 (9)
F3'	0.7860 (3)	0.09262 (18)	0.86974 (18)	0.0964 (8)
C13'	0.8886 (5)	0.2391 (3)	0.6145 (3)	0.0726 (10)
O13'	0.8789 (4)	0.3019 (3)	0.5317 (2)	0.0953 (9)
C14'	0.8891 (7)	0.1121 (3)	0.6241 (3)	0.0989 (14)
H14D	0.8621	0.0961	0.5635	0.148*
H14E	0.7975	0.0886	0.6780	0.148*
H14F	1.0081	0.0701	0.6371	0.148*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0614 (17)	0.0456 (15)	0.0463 (16)	−0.0126 (12)	−0.0084 (13)	0.0007 (12)
N2	0.077 (2)	0.0473 (16)	0.0473 (16)	−0.0152 (13)	−0.0068 (13)	0.0045 (13)
C3	0.068 (2)	0.0430 (18)	0.054 (2)	−0.0103 (16)	−0.0102 (17)	−0.0010 (16)
C4	0.055 (2)	0.0486 (18)	0.053 (2)	−0.0092 (15)	−0.0099 (15)	−0.0037 (15)
C5	0.055 (2)	0.056 (2)	0.0487 (19)	−0.0117 (16)	−0.0067 (15)	−0.0035 (16)
O5	0.0961 (19)	0.0660 (15)	0.0460 (13)	−0.0251 (13)	−0.0112 (12)	0.0044 (11)
C6	0.050 (2)	0.0445 (18)	0.056 (2)	−0.0085 (14)	−0.0029 (15)	−0.0060 (15)
C7	0.077 (3)	0.055 (2)	0.066 (2)	−0.0159 (18)	−0.0112 (19)	0.0008 (18)
C8	0.084 (3)	0.050 (2)	0.086 (3)	−0.0157 (19)	−0.011 (2)	0.002 (2)
C9	0.073 (3)	0.052 (2)	0.098 (3)	−0.0164 (18)	−0.002 (2)	−0.019 (2)
C10	0.086 (3)	0.064 (2)	0.070 (2)	−0.022 (2)	−0.006 (2)	−0.018 (2)
C11	0.079 (3)	0.054 (2)	0.057 (2)	−0.0170 (18)	−0.0042 (18)	−0.0073 (17)
C12	0.107 (4)	0.053 (2)	0.064 (3)	−0.017 (2)	−0.013 (3)	−0.002 (2)
F1	0.244 (5)	0.0707 (18)	0.0569 (19)	−0.053 (2)	−0.025 (2)	0.0120 (14)
F1''	0.18 (2)	0.10 (2)	0.07 (2)	−0.04 (2)	−0.05 (2)	0.033 (19)
F2	0.137 (3)	0.0565 (17)	0.121 (3)	0.0069 (18)	−0.022 (2)	0.0097 (16)
F2''	0.15 (3)	0.059 (18)	0.12 (2)	−0.049 (19)	−0.05 (2)	0.007 (16)
F3	0.118 (3)	0.087 (2)	0.135 (3)	−0.059 (2)	−0.030 (2)	0.023 (2)
F3''	0.14 (2)	0.060 (18)	0.08 (2)	−0.040 (17)	−0.042 (19)	0.052 (16)
C13	0.064 (2)	0.062 (2)	0.069 (2)	−0.0067 (17)	−0.0114 (18)	−0.0165 (19)
O13	0.118 (2)	0.0789 (18)	0.0542 (16)	−0.0138 (15)	−0.0083 (15)	−0.0153 (14)
C14	0.107 (3)	0.064 (2)	0.093 (3)	−0.014 (2)	−0.018 (2)	−0.032 (2)
N1'	0.0623 (18)	0.0467 (16)	0.0565 (17)	−0.0101 (13)	−0.0075 (14)	−0.0023 (13)
N2'	0.0710 (19)	0.0489 (17)	0.0611 (18)	−0.0104 (14)	−0.0097 (14)	−0.0021 (14)
C3'	0.057 (2)	0.049 (2)	0.070 (2)	−0.0112 (16)	−0.0084 (17)	−0.0059 (17)
C4'	0.057 (2)	0.057 (2)	0.061 (2)	−0.0148 (16)	−0.0053 (17)	−0.0095 (17)
C5'	0.053 (2)	0.061 (2)	0.054 (2)	−0.0096 (16)	−0.0055 (16)	−0.0046 (17)
O5'	0.0982 (19)	0.0699 (16)	0.0563 (15)	−0.0246 (14)	−0.0168 (13)	0.0045 (13)
C6'	0.0479 (19)	0.0483 (19)	0.062 (2)	−0.0051 (15)	−0.0083 (16)	−0.0067 (16)
C7'	0.070 (2)	0.054 (2)	0.067 (2)	−0.0113 (17)	−0.0032 (18)	−0.0036 (18)
C8'	0.077 (3)	0.050 (2)	0.088 (3)	−0.0139 (18)	−0.008 (2)	0.002 (2)
C9'	0.080 (3)	0.057 (2)	0.102 (3)	−0.0088 (19)	−0.022 (2)	−0.020 (2)
C10'	0.089 (3)	0.065 (3)	0.080 (3)	−0.008 (2)	−0.021 (2)	−0.019 (2)
C11'	0.072 (2)	0.058 (2)	0.064 (2)	−0.0108 (18)	−0.0118 (18)	−0.0035 (18)
C12'	0.086 (3)	0.056 (2)	0.080 (3)	−0.015 (2)	−0.017 (2)	−0.008 (2)
F1'	0.1063 (19)	0.0639 (14)	0.130 (2)	0.0090 (13)	−0.0078 (16)	−0.0090 (14)
F2'	0.175 (3)	0.0663 (14)	0.0878 (18)	−0.0275 (15)	−0.0512 (17)	0.0124 (13)
F3'	0.1083 (19)	0.0687 (14)	0.1132 (18)	−0.0376 (13)	−0.0114 (14)	0.0012 (13)
C13'	0.073 (3)	0.075 (3)	0.075 (3)	−0.024 (2)	−0.006 (2)	−0.016 (2)
O13'	0.131 (3)	0.098 (2)	0.0654 (18)	−0.0395 (18)	−0.0116 (17)	−0.0173 (16)
C14'	0.125 (4)	0.083 (3)	0.104 (3)	−0.031 (3)	−0.018 (3)	−0.036 (3)

Geometric parameters (Å, º) top

N1—C5	1.353 (4)	C14—H14C	0.9600
N1—N2	1.378 (3)	N1'—C5'	1.354 (4)
N1—C6	1.432 (4)	N1'—N2'	1.374 (3)
N2—C3	1.312 (4)	N1'—C6'	1.432 (4)
C3—C4	1.413 (4)	N2'—C3'	1.308 (4)
C3—C12	1.488 (5)	C3'—C4'	1.416 (5)
C4—C5	1.392 (4)	C3'—C12'	1.499 (5)
C4—C13	1.440 (5)	C4'—C5'	1.390 (4)
C5—O5	1.311 (4)	C4'—C13'	1.445 (5)
O5—H5	1.1757	C5'—O5'	1.306 (4)
C6—C11	1.375 (4)	O5'—H5'	1.0662
C6—C7	1.376 (4)	C6'—C7'	1.377 (4)
C7—C8	1.377 (5)	C6'—C11'	1.385 (4)
C7—H7	0.9300	C7'—C8'	1.368 (5)
C8—C9	1.364 (5)	C7'—H7'	0.9300
C8—H8	0.9300	C8'—C9'	1.371 (5)
C9—C10	1.373 (5)	C8'—H8'	0.9300
C9—H9	0.9300	C9'—C10'	1.364 (5)
C10—C11	1.383 (4)	C9'—H9'	0.9300
C10—H10	0.9300	C10'—C11'	1.380 (5)
C11—H11	0.9300	C10'—H10'	0.9300
C12—F3''	1.22 (3)	C11'—H11'	0.9300
C12—F1''	1.24 (3)	C12'—F2'	1.317 (4)
C12—F2''	1.26 (3)	C12'—F3'	1.324 (4)
C12—F3	1.315 (5)	C12'—F1'	1.335 (4)
C12—F1	1.323 (5)	C13'—O13'	1.246 (4)
C12—F2	1.331 (5)	C13'—C14'	1.494 (5)
C13—O13	1.249 (4)	C14'—H14D	0.9600
C13—C14	1.486 (5)	C14'—H14E	0.9600
C14—H14A	0.9600	C14'—H14F	0.9600
C14—H14B	0.9600

C5—N1—N2	109.9 (2)	C13—C14—H14C	109.5
C5—N1—C6	130.8 (3)	H14A—C14—H14C	109.5
N2—N1—C6	119.3 (2)	H14B—C14—H14C	109.5
C3—N2—N1	105.6 (2)	C5'—N1'—N2'	110.4 (3)
N2—C3—C4	112.9 (3)	C5'—N1'—C6'	130.3 (3)
N2—C3—C12	116.8 (3)	N2'—N1'—C6'	119.2 (3)
C4—C3—C12	130.3 (3)	C3'—N2'—N1'	105.4 (3)
C5—C4—C3	102.8 (3)	N2'—C3'—C4'	113.0 (3)
C5—C4—C13	119.1 (3)	N2'—C3'—C12'	117.5 (3)
C3—C4—C13	138.1 (3)	C4'—C3'—C12'	129.4 (3)
O5—C5—N1	123.7 (3)	C5'—C4'—C3'	102.8 (3)
O5—C5—C4	127.5 (3)	C5'—C4'—C13'	119.1 (3)
N1—C5—C4	108.8 (3)	C3'—C4'—C13'	138.1 (3)
C5—O5—H5	100.5	O5'—C5'—N1'	123.6 (3)
C11—C6—C7	120.5 (3)	O5'—C5'—C4'	127.9 (3)
C11—C6—N1	118.4 (3)	N1'—C5'—C4'	108.4 (3)
C7—C6—N1	121.1 (3)	C5'—O5'—H5'	104.8
C6—C7—C8	119.0 (3)	C7'—C6'—C11'	120.1 (3)
C6—C7—H7	120.5	C7'—C6'—N1'	121.2 (3)
C8—C7—H7	120.5	C11'—C6'—N1'	118.7 (3)
C9—C8—C7	121.4 (4)	C8'—C7'—C6'	119.8 (3)
C9—C8—H8	119.3	C8'—C7'—H7'	120.1
C7—C8—H8	119.3	C6'—C7'—H7'	120.1
C8—C9—C10	119.0 (3)	C7'—C8'—C9'	120.6 (3)
C8—C9—H9	120.5	C7'—C8'—H8'	119.7
C10—C9—H9	120.5	C9'—C8'—H8'	119.7
C9—C10—C11	120.8 (4)	C10'—C9'—C8'	119.8 (4)
C9—C10—H10	119.6	C10'—C9'—H9'	120.1
C11—C10—H10	119.6	C8'—C9'—H9'	120.1
C6—C11—C10	119.2 (3)	C9'—C10'—C11'	120.7 (4)
C6—C11—H11	120.4	C9'—C10'—H10'	119.6
C10—C11—H11	120.4	C11'—C10'—H10'	119.6
F3''—C12—F1''	110.4 (15)	C10'—C11'—C6'	119.1 (3)
F3''—C12—F2''	106.8 (15)	C10'—C11'—H11'	120.5
F1''—C12—F2''	105.9 (17)	C6'—C11'—H11'	120.5
F3—C12—F1	107.1 (4)	F2'—C12'—F3'	106.7 (3)
F3—C12—F2	106.0 (4)	F2'—C12'—F1'	107.2 (3)
F1—C12—F2	105.5 (4)	F3'—C12'—F1'	105.9 (3)
F3''—C12—C3	107.1 (14)	F2'—C12'—C3'	112.6 (3)
F1''—C12—C3	109.2 (19)	F3'—C12'—C3'	112.7 (3)
F2''—C12—C3	117.4 (19)	F1'—C12'—C3'	111.3 (3)
F3—C12—C3	113.5 (4)	O13'—C13'—C4'	118.0 (3)
F1—C12—C3	113.1 (3)	O13'—C13'—C14'	119.2 (4)
F2—C12—C3	111.1 (3)	C4'—C13'—C14'	122.9 (4)
O13—C13—C4	117.9 (3)	C13'—C14'—H14D	109.5
O13—C13—C14	118.9 (3)	C13'—C14'—H14E	109.5
C4—C13—C14	123.1 (3)	H14D—C14'—H14E	109.5
C13—C14—H14A	109.5	C13'—C14'—H14F	109.5
C13—C14—H14B	109.5	H14D—C14'—H14F	109.5
H14A—C14—H14B	109.5	H14E—C14'—H14F	109.5

C5—N1—N2—C3	0.0 (3)	C3—C4—C13—O13	179.8 (4)
C6—N1—N2—C3	178.1 (3)	C5—C4—C13—C14	179.1 (3)
N1—N2—C3—C4	0.4 (4)	C3—C4—C13—C14	−0.8 (6)
N1—N2—C3—C12	−178.7 (3)	C5'—N1'—N2'—C3'	0.1 (3)
N2—C3—C4—C5	−0.6 (4)	C6'—N1'—N2'—C3'	−176.9 (3)
C12—C3—C4—C5	178.3 (4)	N1'—N2'—C3'—C4'	0.0 (4)
N2—C3—C4—C13	179.3 (4)	N1'—N2'—C3'—C12'	177.4 (3)
C12—C3—C4—C13	−1.9 (7)	N2'—C3'—C4'—C5'	0.0 (4)
N2—N1—C5—O5	178.9 (3)	C12'—C3'—C4'—C5'	−177.1 (3)
C6—N1—C5—O5	1.1 (5)	N2'—C3'—C4'—C13'	179.4 (4)
N2—N1—C5—C4	−0.4 (4)	C12'—C3'—C4'—C13'	2.3 (7)
C6—N1—C5—C4	−178.2 (3)	N2'—N1'—C5'—O5'	179.5 (3)
C3—C4—C5—O5	−178.6 (3)	C6'—N1'—C5'—O5'	−3.9 (5)
C13—C4—C5—O5	1.4 (5)	N2'—N1'—C5'—C4'	−0.1 (4)
C3—C4—C5—N1	0.6 (3)	C6'—N1'—C5'—C4'	176.5 (3)
C13—C4—C5—N1	−179.3 (3)	C3'—C4'—C5'—O5'	−179.5 (3)
C5—N1—C6—C11	167.1 (3)	C13'—C4'—C5'—O5'	0.9 (5)
N2—N1—C6—C11	−10.6 (4)	C3'—C4'—C5'—N1'	0.1 (4)
C5—N1—C6—C7	−13.6 (5)	C13'—C4'—C5'—N1'	−179.5 (3)
N2—N1—C6—C7	168.8 (3)	C5'—N1'—C6'—C7'	−16.1 (5)
C11—C6—C7—C8	−0.2 (5)	N2'—N1'—C6'—C7'	160.2 (3)
N1—C6—C7—C8	−179.6 (3)	C5'—N1'—C6'—C11'	165.3 (3)
C6—C7—C8—C9	0.9 (6)	N2'—N1'—C6'—C11'	−18.4 (4)
C7—C8—C9—C10	−1.0 (6)	C11'—C6'—C7'—C8'	0.8 (5)
C8—C9—C10—C11	0.5 (6)	N1'—C6'—C7'—C8'	−177.7 (3)
C7—C6—C11—C10	−0.3 (5)	C6'—C7'—C8'—C9'	0.1 (6)
N1—C6—C11—C10	179.0 (3)	C7'—C8'—C9'—C10'	−0.8 (6)
C9—C10—C11—C6	0.2 (5)	C8'—C9'—C10'—C11'	0.6 (6)
N2—C3—C12—F3''	−59 (3)	C9'—C10'—C11'—C6'	0.4 (6)
C4—C3—C12—F3''	122 (3)	C7'—C6'—C11'—C10'	−1.1 (5)
N2—C3—C12—F1''	60 (3)	N1'—C6'—C11'—C10'	177.5 (3)
C4—C3—C12—F1''	−119 (3)	N2'—C3'—C12'—F2'	−2.5 (5)
N2—C3—C12—F2''	−179 (3)	C4'—C3'—C12'—F2'	174.5 (4)
C4—C3—C12—F2''	2 (3)	N2'—C3'—C12'—F3'	118.3 (4)
N2—C3—C12—F3	−122.2 (5)	C4'—C3'—C12'—F3'	−64.8 (5)
C4—C3—C12—F3	59.0 (6)	N2'—C3'—C12'—F1'	−122.9 (4)
N2—C3—C12—F1	0.0 (6)	C4'—C3'—C12'—F1'	54.0 (5)
C4—C3—C12—F1	−178.9 (4)	C5'—C4'—C13'—O13'	0.7 (5)
N2—C3—C12—F2	118.4 (4)	C3'—C4'—C13'—O13'	−178.6 (4)
C4—C3—C12—F2	−60.4 (6)	C5'—C4'—C13'—C14'	180.0 (4)
C5—C4—C13—O13	−0.3 (5)	C3'—C4'—C13'—C14'	0.7 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O13	1.18	1.60	2.548 (3)	132
O5′—H5′···O13′	1.07	1.65	2.560 (4)	139
C14—H14B···F1′ⁱ	0.96	2.55	3.394 (5)	146
C7—H7···O13ⁱⁱ	0.93	2.64	3.446 (4)	145
C7′—H7′···O13′ⁱⁱⁱ	0.93	2.57	3.406 (4)	149

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

Experimental details

Crystal data
Chemical formula	C₁₂H₉F₃N₂O₂
M_r	270.21
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.4779 (19), 11.9390 (18), 13.8587 (14)
α, β, γ (°)	78.591 (11), 80.090 (17), 78.791 (18)
V (Å³)	1178.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.40 × 0.33 × 0.13

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4766, 4567, 2268
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.165, 1.04
No. of reflections	4567
No. of parameters	373
No. of restraints	81
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.21

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), HELENA (Spek, 1996), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O13	1.18	1.60	2.548 (3)	132
O5'—H5'···O13'	1.07	1.65	2.560 (4)	139
C14—H14B···F1'ⁱ	0.96	2.55	3.394 (5)	146
C7—H7···O13ⁱⁱ	0.93	2.64	3.446 (4)	145
C7'—H7'···O13'ⁱⁱⁱ	0.93	2.57	3.406 (4)	149

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

Acknowledgements

The authors are grateful to the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and the Instituto Nacional de Ciência e Tecnologia (INCT) - Catálize for financial assistance.

References

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