5-Hy­droxy-3-phenyl-5-trifluoro­meth­yl-4,5-dihydro-1H-pyrazole

Asiri, A.M.; Al-Youbi, A.O.; Faidallah, H.M.; Ng, S.W.

doi:10.1107/S160053681103368X

organic compounds

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Volume 67| Part 9| September 2011| Page o2442

doi:10.1107/S160053681103368X

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5-Hydroxy-3-phenyl-5-trifluoromethyl-4,5-dihydro-1H-pyrazole

Abdullah M. Asiri,^a,^b Abdulrahman O. Al-Youbi,^a Hassan M. Faidallah ^a and Seik Weng Ng ^c ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia, ^bCenter of Excellence for Advanced Materials Research, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 17 August 2011; accepted 18 August 2011; online 27 August 2011)

The five-membered dihydropyrazole ring in the title compound, C₁₀H₉F₃N₂O, is approximately planar (r.m.s. deviation 0.111 Å for all non-H atoms) and its phenyl substituent is aligned at an angle of 14.7 (2)°. Adjacent molecules are linked by N—H⋯O and O—H⋯N hydrogen bonds, generating ribbons running along the b axis of the monoclinic unit cell.

Related literature

For the synthesis, see: Yakimovich et al. (2002 ); Zelenin et al. (1995 ). For two related structures, see: Dias & Goh (2004 ); Yang & Raptis (2003 ).

Experimental

Crystal data

C₁₀H₉F₃N₂O
M_r = 230.19
Monoclinic, P 2₁
a = 9.1000 (6) Å
b = 5.4032 (3) Å
c = 10.4515 (7) Å
β = 108.139 (7)°
V = 488.35 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 100 K
0.20 × 0.15 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.972, T_max = 0.986
4222 measured reflections
1230 independent reflections
1060 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.087
S = 1.05
1230 reflections
153 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.84 (1)	2.03 (2)	2.833 (3)	162 (4)
N2—H2⋯O1ⁱⁱ	0.88 (1)	2.13 (2)	2.974 (3)	161 (3)
Symmetry codes: (i) x, y-1, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681103368X/bt5617sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681103368X/bt5617Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681103368X/bt5617Isup3.cml

checkCIF report

Comment top

We had intended to synthesize 5-phenyl-3-(trifluoromethyl)pyrazole, whose crystal structure has been reported (Dias & Goh, 2004). However, the strongly electron-withdrawing nature of the α,β-diketone used in the synthesis led to the isolation of a stable intermediate, a dihydropyrazole (Scheme I), that when dehydrated, should furnish the pyrazole. The synthesis of the dihydropyrazole has previously been reported (Yakimovich et al., 2002; Zelenin et al., 1995). The five-membered dihydropyrazole ring of C₁₀H₉F₃N₂O is approximately planar, the ring being buckled at the methylene carbon, and its phenyl substituent is aligned at 14.7 (2)° (Fig. 1). Adjacent molecules are linked by N—H···O and O—H···N hydrogen bonds (Table 1) to generate a helical chain running along the b axis of the monoclinic unit cell (Fig. 2).

The crystal structure of the 2-naphthyl substituted analog has been reported (Yang & Raptis, 2003); both compounds should similar hydrogen-bonding features.

Related literature top

For the synthesis, see: Yakimovich et al. (2002); Zelenin et al. (1995). For two related structures, see: Dias & Goh (2004); Yang & Raptis (2003).

Experimental top

4,4,4-Trifluoro-1-phenyl-1,3-butanedione (10 mmol) in ethanol (50 ml) was refluxed with hydrazine hydrate (10 mmol) for 4 h. Water was added to precipitate the product, which was collected and recrystallized from ethanol; m.p. 415–416 K.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₁₀H₉F₃N₂O at the 70% probability level; H atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Hydrogen-bonded ribbon structure.

5-Hydroxy-3-phenyl-5-trifluoromethyl-4,5-dihydro-1H-pyrazole top

Crystal data top

C₁₀H₉F₃N₂O	F(000) = 236
M_r = 230.19	D_x = 1.565 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1825 reflections
a = 9.1000 (6) Å	θ = 2.4–29.2°
b = 5.4032 (3) Å	µ = 0.14 mm⁻¹
c = 10.4515 (7) Å	T = 100 K
β = 108.139 (7)°	Prism, colourless
V = 488.35 (5) Å³	0.20 × 0.15 × 0.10 mm
Z = 2

Data collection top

Agilent SuperNova Dual diffractometer with Atlas detector	1230 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1060 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.039
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.4°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −6→6
T_min = 0.972, T_max = 0.986	l = −13→13
4222 measured reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0412P)² + 0.1359P] where P = (F_o² + 2F_c²)/3
1230 reflections	(Δ/σ)_max = 0.001
153 parameters	Δρ_max = 0.29 e Å⁻³
3 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₀H₉F₃N₂O	V = 488.35 (5) Å³
M_r = 230.19	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 9.1000 (6) Å	µ = 0.14 mm⁻¹
b = 5.4032 (3) Å	T = 100 K
c = 10.4515 (7) Å	0.20 × 0.15 × 0.10 mm
β = 108.139 (7)°

Data collection top

Agilent SuperNova Dual diffractometer with Atlas detector	1230 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1060 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.986	R_int = 0.039
4222 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	3 restraints
wR(F²) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.29 e Å⁻³
1230 reflections	Δρ_min = −0.26 e Å⁻³
153 parameters

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

	x	y	z	U_iso*/U_eq
F1	0.15155 (18)	0.5006 (3)	0.41240 (17)	0.0224 (4)
F2	0.07047 (18)	0.8747 (4)	0.36876 (17)	0.0275 (4)
F3	0.27744 (19)	0.7556 (3)	0.32684 (15)	0.0239 (4)
O1	0.4291 (2)	0.6574 (4)	0.59470 (19)	0.0147 (4)
H1	0.407 (4)	0.534 (5)	0.634 (4)	0.045 (12)*
N1	0.3514 (3)	1.1846 (4)	0.6715 (2)	0.0148 (5)
N2	0.3409 (3)	1.0670 (4)	0.5493 (2)	0.0147 (5)
H2	0.425 (2)	1.094 (6)	0.526 (3)	0.026 (9)*
C1	0.2622 (3)	1.1255 (5)	0.8657 (3)	0.0147 (6)
C2	0.1637 (3)	0.9892 (6)	0.9190 (3)	0.0177 (6)
H2A	0.1048	0.8565	0.8688	0.021*
C3	0.1519 (3)	1.0472 (6)	1.0446 (3)	0.0209 (6)
H3	0.0860	0.9528	1.0807	0.025*
C4	0.2358 (3)	1.2421 (6)	1.1175 (3)	0.0226 (7)
H4	0.2278	1.2809	1.2037	0.027*
C5	0.3317 (3)	1.3813 (6)	1.0650 (3)	0.0212 (6)
H5	0.3879	1.5167	1.1148	0.025*
C6	0.3455 (3)	1.3230 (5)	0.9398 (3)	0.0188 (6)
H6	0.4119	1.4179	0.9045	0.023*
C7	0.2782 (3)	1.0531 (5)	0.7351 (3)	0.0144 (6)
C8	0.2110 (3)	0.8206 (5)	0.6601 (3)	0.0141 (6)
H8A	0.0979	0.8347	0.6169	0.017*
H8B	0.2338	0.6738	0.7197	0.017*
C9	0.2974 (3)	0.8121 (5)	0.5561 (3)	0.0140 (6)
C10	0.1981 (3)	0.7364 (5)	0.4152 (3)	0.0167 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0249 (9)	0.0185 (9)	0.0224 (8)	−0.0067 (7)	0.0054 (7)	−0.0054 (7)
F2	0.0243 (9)	0.0285 (10)	0.0233 (9)	0.0091 (8)	−0.0019 (7)	0.0000 (8)
F3	0.0318 (9)	0.0273 (10)	0.0154 (8)	−0.0024 (8)	0.0116 (7)	−0.0015 (7)
O1	0.0157 (9)	0.0121 (10)	0.0179 (10)	0.0015 (8)	0.0073 (8)	0.0027 (8)
N1	0.0202 (12)	0.0116 (11)	0.0136 (11)	0.0025 (9)	0.0068 (9)	0.0018 (9)
N2	0.0204 (12)	0.0094 (11)	0.0181 (11)	−0.0013 (10)	0.0116 (9)	−0.0008 (9)
C1	0.0162 (12)	0.0127 (14)	0.0148 (13)	0.0027 (11)	0.0045 (10)	0.0019 (11)
C2	0.0196 (13)	0.0168 (14)	0.0181 (13)	0.0000 (12)	0.0079 (11)	−0.0017 (11)
C3	0.0241 (14)	0.0242 (17)	0.0173 (14)	0.0020 (13)	0.0107 (12)	0.0030 (13)
C4	0.0278 (15)	0.0247 (17)	0.0151 (13)	0.0054 (14)	0.0065 (11)	−0.0013 (13)
C5	0.0220 (14)	0.0196 (15)	0.0212 (15)	0.0026 (13)	0.0054 (12)	−0.0042 (12)
C6	0.0190 (13)	0.0170 (15)	0.0202 (14)	0.0016 (12)	0.0059 (11)	0.0000 (12)
C7	0.0138 (12)	0.0120 (13)	0.0173 (13)	0.0011 (11)	0.0048 (10)	−0.0003 (11)
C8	0.0163 (12)	0.0129 (15)	0.0156 (13)	−0.0001 (11)	0.0086 (10)	0.0000 (11)
C9	0.0145 (12)	0.0130 (15)	0.0155 (13)	0.0013 (11)	0.0061 (10)	0.0002 (11)
C10	0.0209 (14)	0.0141 (15)	0.0154 (13)	0.0002 (12)	0.0061 (10)	0.0007 (12)

Geometric parameters (Å, º) top

F1—C10	1.340 (3)	C2—H2A	0.9500
F2—C10	1.338 (3)	C3—C4	1.382 (4)
F3—C10	1.342 (3)	C3—H3	0.9500
O1—C9	1.413 (3)	C4—C5	1.387 (4)
O1—H1	0.836 (10)	C4—H4	0.9500
N1—C7	1.290 (3)	C5—C6	1.389 (4)
N1—N2	1.403 (3)	C5—H5	0.9500
N2—C9	1.441 (4)	C6—H6	0.9500
N2—H2	0.882 (10)	C7—C8	1.505 (4)
C1—C6	1.396 (4)	C8—C9	1.528 (4)
C1—C2	1.403 (4)	C8—H8A	0.9900
C1—C7	1.471 (4)	C8—H8B	0.9900
C2—C3	1.386 (4)	C9—C10	1.524 (4)

C9—O1—H1	107 (3)	C1—C6—H6	119.9
C7—N1—N2	108.6 (2)	N1—C7—C1	123.2 (3)
N1—N2—C9	109.3 (2)	N1—C7—C8	112.5 (2)
N1—N2—H2	111 (2)	C1—C7—C8	124.3 (2)
C9—N2—H2	116 (2)	C7—C8—C9	100.4 (2)
C6—C1—C2	119.0 (3)	C7—C8—H8A	111.7
C6—C1—C7	121.7 (3)	C9—C8—H8A	111.7
C2—C1—C7	119.3 (3)	C7—C8—H8B	111.7
C3—C2—C1	120.4 (3)	C9—C8—H8B	111.7
C3—C2—H2A	119.8	H8A—C8—H8B	109.5
C1—C2—H2A	119.8	O1—C9—N2	111.0 (2)
C4—C3—C2	120.1 (3)	O1—C9—C10	108.2 (2)
C4—C3—H3	120.0	N2—C9—C10	107.4 (2)
C2—C3—H3	120.0	O1—C9—C8	113.2 (2)
C3—C4—C5	120.2 (3)	N2—C9—C8	102.5 (2)
C3—C4—H4	119.9	C10—C9—C8	114.4 (2)
C5—C4—H4	119.9	F2—C10—F1	106.9 (2)
C4—C5—C6	120.1 (3)	F2—C10—F3	107.4 (2)
C4—C5—H5	119.9	F1—C10—F3	107.0 (2)
C6—C5—H5	119.9	F2—C10—C9	112.8 (2)
C5—C6—C1	120.2 (3)	F1—C10—C9	111.4 (2)
C5—C6—H6	119.9	F3—C10—C9	111.1 (2)

C7—N1—N2—C9	−18.0 (3)	C1—C7—C8—C9	−166.2 (2)
C6—C1—C2—C3	−1.3 (4)	N1—N2—C9—O1	−95.1 (2)
C7—C1—C2—C3	177.2 (2)	N1—N2—C9—C10	146.8 (2)
C1—C2—C3—C4	0.8 (4)	N1—N2—C9—C8	25.9 (3)
C2—C3—C4—C5	0.3 (4)	C7—C8—C9—O1	96.5 (2)
C3—C4—C5—C6	−1.0 (4)	C7—C8—C9—N2	−23.0 (2)
C4—C5—C6—C1	0.5 (4)	C7—C8—C9—C10	−138.9 (2)
C2—C1—C6—C5	0.6 (4)	O1—C9—C10—F2	−179.4 (2)
C7—C1—C6—C5	−177.8 (2)	N2—C9—C10—F2	−59.5 (3)
N2—N1—C7—C1	−178.3 (2)	C8—C9—C10—F2	53.5 (3)
N2—N1—C7—C8	1.3 (3)	O1—C9—C10—F1	60.5 (3)
C6—C1—C7—N1	−10.1 (4)	N2—C9—C10—F1	−179.7 (2)
C2—C1—C7—N1	171.5 (2)	C8—C9—C10—F1	−66.7 (3)
C6—C1—C7—C8	170.4 (2)	O1—C9—C10—F3	−58.7 (3)
C2—C1—C7—C8	−8.0 (4)	N2—C9—C10—F3	61.1 (3)
N1—C7—C8—C9	14.3 (3)	C8—C9—C10—F3	174.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.84 (1)	2.03 (2)	2.833 (3)	162 (4)
N2—H2···O1ⁱⁱ	0.88 (1)	2.13 (2)	2.974 (3)	161 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₀H₉F₃N₂O
M_r	230.19
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	9.1000 (6), 5.4032 (3), 10.4515 (7)
β (°)	108.139 (7)
V (Å³)	488.35 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.972, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	4222, 1230, 1060
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.087, 1.05
No. of reflections	1230
No. of parameters	153
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.26

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.84 (1)	2.03 (2)	2.833 (3)	162 (4)
N2—H2···O1ⁱⁱ	0.88 (1)	2.13 (2)	2.974 (3)	161 (3)

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

Acknowledgements

The authors thank King Abdulaziz University and the University of Malaya for supporting this study.

References

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