2-Phenyl-5-(trifluoro-meth-yl)pyrazol-3(2H)-one.

The title compound, C(10)H(7)F(3)N(2)O, is an analogue of pyrazolone derivatives with potential analgesic and anti-inflammatory properties. Its mol-ecular structure consists of phenyl and pyrazol-3(2H)-one units with a dihedral angle between the mean planes of the rings of 33.0 (1)°. The crystal structure is stabilized by an inter-molecular hydrogen bond between the N-H group and the carbonyl O atom of the pyrazol-3(2H)-one ring which links the mol-ecules into supra-molecular C(5) chains along [001] and by weak π-π stacking inter-actions between the phenyl rings [centroid-centroid distance = 3.881 (2) Å]. The F atoms are disordered over two positions with refined site occupancies of 0.768(11) and 0.232(11).

Related literature

For the analgesic properties of pyrazolones, see: Mehlisch (1983 ▶); Schnitzer (2003 ▶). For the biological activity of some pyrazolone derivatives, see: Pavlov et al. (1998 ▶). For the pharmacological properties of pyrazolone deriavtives, see: Kees et al. (1996 ▶). For related structures, see: Belmar et al. (2006a ▶,b ▶); Pérez et al. (2005 ▶). For metal complexes, see: Hyun-Shin et al. (2008 ▶); Gallardo et al. (2004 ▶); Meyer et al. (1998 ▶). For the synthesis of pyrazolones, see: Nakagawa et al. (2006 ▶); Belmar et al. (2001 ▶); Bartulín et al. (1994 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C10H7F3N2O

M = 228.18

Monoclinic,

a = 5.8409 (5) Å

b = 15.2454 (14) Å

c = 11.2291 (17) Å

β = 92.403 (9)°

V = 999.0 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.14 mm−1

T = 293 K

0.46 × 0.40 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: none

2262 measured reflections

2157 independent reflections

1141 reflections with I > 2σ(I)

R int = 0.024

3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.188

S = 1.03

2157 reflections

173 parameters

81 restraints

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.32 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: SET4 in CAD-4 Software; data reduction: HELENA (Spek, 1996 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029419/bx2225sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029419/bx2225Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C10H7F3N2O	F(000) = 464
Mr = 228.18	Dx = 1.517 Mg m−3
Monoclinic, P21/c	Melting point = 464–465 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 5.8409 (5) Å	Cell parameters from 25 reflections
b = 15.2454 (14) Å	θ = 3.2–13.8°
c = 11.2291 (17) Å	µ = 0.14 mm−1
β = 92.403 (9)°	T = 293 K
V = 999.0 (2) Å3	Irregular, colourless
Z = 4	0.46 × 0.40 × 0.20 mm

Enraf–Nonius CAD-4 diffractometer	Rint = 0.024
Radiation source: fine-focus sealed tube	θmax = 27.0°, θmin = 2.3°
graphite	h = −7→7
ω–2θ scans	k = −19→0
2262 measured reflections	l = −14→0
2157 independent reflections	3 standard reflections every 200 reflections
1141 reflections with I > 2σ(I)	intensity decay: 1%

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.188	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0843P)2 + 0.3445P] where P = (Fo2 + 2Fc2)/3
2157 reflections	(Δ/σ)max = 0.001
173 parameters	Δρmax = 0.30 e Å−3
81 restraints	Δρmin = −0.32 e Å−3

Experimental. The title compound was synthesized by the condensation of ethyl 4,4,4-trifluoroacetoacetate (5.0?g, 27.2?mmol) in acetic acid (50?ml) with phenylhydrazine (2.9?g, 27.2?mmol) which was added drop wise, with stirring for 3?h. The solvent was removed by evaporation; resulting crude solid was extracted with AcOEt. The organic layer was washed with saturated aqueous NaHCO3 and water, then brine, and evaporation the solvent. The compound, obtained as colorless single crystals, was recrystallized using ethylacetate and n-hexane (2:1) and was suitable for X-ray structure determination. Yield 76% mp: 191–192 °C, lit. 195–196 °C (Nakagawa et al., 2006). 1H-NMR (DMSO, 400?MHz, d, p.p.m.) 12,42 (1H, s), 7,70 (2H, d, J = 8?Hz), 7,49 (2H, t, J = 8?Hz), 7,36 (1H, t, J = 8?Hz), 5,92 (1H, s). 13C-NMR (DMSO, 400?MHz, d, p.p.m.) 153,68 (C5), 140,21 (C3), 13,70 (C6), 129,07 (C10; C8), 127,18 (C9), 122,25 (C11; C7), 119,98 (C12), 85,53 (C4).

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.2789 (5)	0.78258 (17)	0.98039 (19)	0.0486 (7)
N2	0.3999 (5)	0.73266 (19)	0.90418 (19)	0.0534 (7)
H2	0.3729	0.7405	0.8270	0.064*
C3	0.5425 (6)	0.6863 (2)	0.9721 (3)	0.0535 (8)
C4	0.5221 (6)	0.7045 (2)	1.0923 (3)	0.0567 (9)
H4	0.6052	0.6801	1.1566	0.068*
C5	0.3528 (6)	0.7661 (2)	1.0950 (2)	0.0523 (8)
C6	0.1101 (5)	0.8436 (2)	0.9370 (2)	0.0471 (8)
C7	0.1383 (6)	0.8843 (2)	0.8282 (2)	0.0582 (9)
H7	0.2671	0.8730	0.7847	0.070*
C8	−0.0280 (7)	0.9420 (3)	0.7854 (3)	0.0730 (11)
H8	−0.0111	0.9694	0.7123	0.088*
C9	−0.2193 (7)	0.9594 (3)	0.8499 (4)	0.0745 (11)
H9	−0.3304	0.9983	0.8204	0.089*
C10	−0.2439 (6)	0.9189 (3)	0.9575 (3)	0.0691 (10)
H10	−0.3715	0.9309	1.0016	0.083*
C11	−0.0805 (6)	0.8604 (2)	1.0010 (3)	0.0583 (9)
H11	−0.0994	0.8323	1.0735	0.070*
C12	0.7009 (8)	0.6240 (3)	0.9172 (3)	0.0712 (11)
F1	0.7641 (13)	0.6502 (4)	0.8115 (4)	0.118 (3)	0.768 (11)
F1'	0.617 (3)	0.5831 (17)	0.826 (2)	0.129 (8)	0.232 (11)
F2	0.8938 (12)	0.6159 (7)	0.9809 (5)	0.129 (3)	0.768 (11)
F2'	0.884 (4)	0.6549 (11)	0.882 (3)	0.141 (9)	0.232 (11)
F3	0.6134 (13)	0.5470 (4)	0.9008 (9)	0.144 (3)	0.768 (11)
F3'	0.760 (5)	0.5604 (14)	0.9906 (13)	0.104 (6)	0.232 (11)
O1	0.2602 (4)	0.81041 (16)	1.18269 (16)	0.0686 (8)

	U11	U22	U33	U12	U13	U23
N1	0.0599 (16)	0.0617 (17)	0.0244 (11)	0.0019 (14)	0.0042 (10)	−0.0008 (11)
N2	0.0666 (17)	0.0714 (18)	0.0225 (11)	0.0001 (14)	0.0044 (11)	−0.0034 (11)
C3	0.062 (2)	0.062 (2)	0.0374 (16)	0.0015 (17)	0.0057 (15)	0.0011 (15)
C4	0.068 (2)	0.068 (2)	0.0336 (15)	0.0072 (19)	0.0006 (14)	0.0062 (15)
C5	0.070 (2)	0.063 (2)	0.0242 (14)	−0.0023 (18)	0.0033 (13)	0.0040 (13)
C6	0.0554 (19)	0.0511 (18)	0.0343 (15)	−0.0052 (16)	−0.0026 (13)	−0.0028 (13)
C7	0.072 (2)	0.067 (2)	0.0360 (15)	−0.0042 (19)	0.0003 (15)	0.0052 (15)
C8	0.093 (3)	0.068 (3)	0.056 (2)	−0.011 (2)	−0.015 (2)	0.0164 (18)
C9	0.075 (3)	0.063 (2)	0.083 (3)	0.001 (2)	−0.022 (2)	0.005 (2)
C10	0.059 (2)	0.073 (2)	0.075 (2)	0.001 (2)	−0.0004 (18)	−0.004 (2)
C11	0.062 (2)	0.066 (2)	0.0470 (18)	−0.0056 (19)	0.0017 (16)	0.0011 (16)
C12	0.078 (3)	0.083 (3)	0.054 (2)	0.010 (2)	0.018 (2)	−0.003 (2)
F1	0.142 (6)	0.152 (5)	0.064 (3)	0.052 (4)	0.050 (3)	0.008 (3)
F1'	0.083 (11)	0.172 (19)	0.129 (14)	0.035 (11)	−0.038 (10)	−0.112 (12)
F2	0.100 (4)	0.187 (7)	0.099 (4)	0.068 (4)	−0.016 (3)	−0.030 (4)
F2'	0.105 (13)	0.127 (13)	0.20 (2)	−0.035 (10)	0.083 (14)	−0.071 (15)
F3	0.164 (6)	0.077 (3)	0.197 (8)	−0.008 (3)	0.088 (6)	−0.041 (4)
F3'	0.133 (15)	0.104 (11)	0.074 (8)	0.059 (10)	−0.003 (9)	−0.004 (8)
O1	0.0983 (19)	0.0804 (17)	0.0276 (11)	0.0248 (15)	0.0078 (11)	−0.0044 (10)

N1—C5	1.363 (3)	C8—C9	1.382 (6)
N1—N2	1.365 (3)	C8—H8	0.9300
N1—C6	1.426 (4)	C9—C10	1.371 (5)
N2—C3	1.312 (4)	C9—H9	0.9300
N2—H2	0.8825	C10—C11	1.381 (5)
C3—C4	1.388 (4)	C10—H10	0.9300
C3—C12	1.479 (5)	C11—H11	0.9300
C4—C5	1.366 (5)	C12—F2'	1.247 (14)
C4—H4	0.9300	C12—F1'	1.279 (13)
C5—O1	1.327 (4)	C12—F3	1.291 (7)
C6—C11	1.374 (4)	C12—F3'	1.309 (13)
C6—C7	1.387 (4)	C12—F2	1.315 (6)
C7—C8	1.381 (5)	C12—F1	1.320 (5)
C7—H7	0.9300
C5—N1—N2	109.7 (3)	C9—C8—H8	119.6
C5—N1—C6	129.0 (2)	C10—C9—C8	119.5 (4)
N2—N1—C6	121.2 (2)	C10—C9—H9	120.3
C3—N2—N1	105.6 (2)	C8—C9—H9	120.3
C3—N2—H2	136.6	C9—C10—C11	120.4 (4)
N1—N2—H2	117.7	C9—C10—H10	119.8
N2—C3—C4	112.3 (3)	C11—C10—H10	119.8
N2—C3—C12	119.8 (3)	C6—C11—C10	119.9 (3)
C4—C3—C12	127.9 (3)	C6—C11—H11	120.1
C5—C4—C3	104.5 (3)	C10—C11—H11	120.1
C5—C4—H4	127.7	F2'—C12—F1'	103.5 (9)
C3—C4—H4	127.7	F2'—C12—F3'	105.9 (9)
O1—C5—N1	119.0 (3)	F1'—C12—F3'	103.0 (9)
O1—C5—C4	133.2 (3)	F3—C12—F2	108.5 (5)
N1—C5—C4	107.9 (3)	F3—C12—F1	105.8 (5)
C11—C6—C7	120.4 (3)	F2—C12—F1	104.6 (5)
C11—C6—N1	120.4 (3)	F2'—C12—C3	116.7 (8)
C7—C6—N1	119.2 (3)	F1'—C12—C3	114.9 (7)
C8—C7—C6	118.9 (3)	F3—C12—C3	113.1 (4)
C8—C7—H7	120.5	F3'—C12—C3	111.6 (7)
C6—C7—H7	120.5	F2—C12—C3	111.8 (4)
C7—C8—C9	120.8 (3)	F1—C12—C3	112.5 (4)
C7—C8—H8	119.6
C5—N1—N2—C3	0.6 (4)	C6—C7—C8—C9	0.3 (5)
C6—N1—N2—C3	178.3 (3)	C7—C8—C9—C10	0.0 (6)
N1—N2—C3—C4	−0.6 (4)	C8—C9—C10—C11	−0.7 (6)
N1—N2—C3—C12	179.7 (3)	C7—C6—C11—C10	−0.7 (5)
N2—C3—C4—C5	0.4 (4)	N1—C6—C11—C10	−179.4 (3)
C12—C3—C4—C5	180.0 (4)	C9—C10—C11—C6	1.1 (5)
N2—N1—C5—O1	178.1 (3)	N2—C3—C12—F2'	84.0 (18)
C6—N1—C5—O1	0.6 (5)	C4—C3—C12—F2'	−95.6 (18)
N2—N1—C5—C4	−0.4 (4)	N2—C3—C12—F1'	−37.5 (17)
C6—N1—C5—C4	−177.9 (3)	C4—C3—C12—F1'	143.0 (17)
C3—C4—C5—O1	−178.1 (4)	N2—C3—C12—F3	−88.1 (7)
C3—C4—C5—N1	0.0 (4)	C4—C3—C12—F3	92.3 (7)
C5—N1—C6—C11	−35.3 (5)	N2—C3—C12—F3'	−154.2 (17)
N2—N1—C6—C11	147.5 (3)	C4—C3—C12—F3'	26.3 (18)
C5—N1—C6—C7	146.0 (3)	N2—C3—C12—F2	149.0 (7)
N2—N1—C6—C7	−31.2 (4)	C4—C3—C12—F2	−30.5 (9)
C11—C6—C7—C8	0.0 (5)	N2—C3—C12—F1	31.7 (7)
N1—C6—C7—C8	178.7 (3)	C4—C3—C12—F1	−147.9 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1i	0.88	1.89	2.667 (3)	146

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1i	0.88	1.89	2.667 (3)	146

Symmetry code: (i) .