1-Methyl-5-phen­oxy-3-trifluoro­methyl-1H-pyrazole-4-carbaldehyde oxime

Dai, H.; Miao, W.-K.; Wu, S.-S.; Qin, X.; Fang, J.-X.

doi:10.1107/S1600536811007422

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o775

doi:10.1107/S1600536811007422

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1-Methyl-5-phenoxy-3-trifluoromethyl-1H-pyrazole-4-carbaldehyde oxime

Hong Dai,^a,^b Wen-Ke Miao,^a Shan-Shan Wu,^a Xue Qin ^a and Jian-Xin Fang ^a ^*

^aState Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Nantong University, Nantong 226019, People's Republic of China
^*Correspondence e-mail: daihong_2001@yahoo.com.cn

(Received 13 February 2011; accepted 27 February 2011; online 5 March 2011)

In the title compound, C₁₂H₁₀F₃N₃O₂, the dihedral angle between the phenyl and pyrazole rings is 96.6 (3)°. In the crystal, pairs of O—H⋯N hydrogen bonds link the molecules, forming inversion dimers. Weak intermolecular C—H⋯F hydrogen bonds are also observed.

Related literature

For the biological activity of pyrazole-4-carbaldehyde oxime ether derivatives, see: Hamaguchi et al. (1995 ); Motoba et al. (1992 ).

Experimental

Crystal data

C₁₂H₁₀F₃N₃O₂
M_r = 285.23
Monoclinic, P 2₁ /c
a = 7.5221 (15) Å
b = 18.282 (4) Å
c = 9.1002 (18) Å
β = 90.58 (3)°
V = 1251.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 113 K
0.24 × 0.16 × 0.14 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T_min = 0.968, T_max = 0.981
7050 measured reflections
2185 independent reflections
1910 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.101
S = 1.06
2185 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯F1ⁱ	0.93	2.54	3.147 (2)	123
O2—H2⋯N3ⁱⁱ	0.82	2.11	2.819 (2)	145
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z+1.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811007422/is2677sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811007422/is2677Isup2.hkl

checkCIF report

Comment top

The pyrazole oxime unit plays an important role in many biologically active compounds. A large number of pyrazole oxime derivatives are well acknowledged to possess fungicidal, insecticidal, and acaricidal activities (Hamaguchi et al., 1995). For example, fenpyroximate, a commercial acaricide, has been widely used for the control of mites on many crops (Motoba et al., 1992).

The title compound, (I), is an important intermediate for agrochemicals and drugs. It contains two planes, the pyrazole ring (N2/N1/C2–C4) and the phenyl ring (C5–C10) (Fig. 1). The dihedral angle between the phenyl ring and the pyrazole ring is 96.6 (3)°. In the crystal structure, the molecules are linked by intermolecular C—H···F and O—H···N hydrogen bonds (Table 1 and Fig. 2).

Related literature top

For the biological activity of pyrazole-4-carbaldehyde oxime ether derivatives, see: Hamaguchi et al. (1995); Motoba et al. (1992).

Experimental top

To a stirred solution of hydroxylamine hydrochloride (7.5 mmol) and potassium hydroxide (10 mmol) in ethanol (30 ml), was added 1-methyl-3-(trifluoromethyl)-5-phenoxy-1H-pyrazole-4-carbaldehyde (5 mmol) at room temperature. The resulting mixture was heated to reflux for 3 h. The reaction mixture was poured into water (150 ml) and extracted with ethyl acetate (3 × 40 ml). The organic layer was washed with saturated brine (3 × 20 ml), and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, then the residue was recrystallized from ethyl acetate to give colourless crystals.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A packing diagram of the title compound viewed along the a axis, with hydrogen bonds drawn as dashed lines.

1-Methyl-5-phenoxy-3-trifluoromethyl-1H-pyrazole-4-carbaldehyde oxime top

Crystal data top

C₁₂H₁₀F₃N₃O₂	F(000) = 584
M_r = 285.23	D_x = 1.514 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3687 reflections
a = 7.5221 (15) Å	θ = 2.2–27.9°
b = 18.282 (4) Å	µ = 0.14 mm⁻¹
c = 9.1002 (18) Å	T = 113 K
β = 90.58 (3)°	Monoclinic, colourless
V = 1251.4 (4) Å³	0.24 × 0.16 × 0.14 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	2185 independent reflections
Radiation source: fine-focus sealed tube	1910 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.968, T_max = 0.981	k = −21→21
7050 measured reflections	l = −7→10

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) = 0.101	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0599P)² + 0.3152P] where P = (F_o² + 2F_c²)/3
2185 reflections	(Δ/σ)_max = 0.002
183 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₂H₁₀F₃N₃O₂	V = 1251.4 (4) Å³
M_r = 285.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.5221 (15) Å	µ = 0.14 mm⁻¹
b = 18.282 (4) Å	T = 113 K
c = 9.1002 (18) Å	0.24 × 0.16 × 0.14 mm
β = 90.58 (3)°

Data collection top

Bruker SMART 1000 CCD diffractometer	2185 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1910 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.981	R_int = 0.030
7050 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.06	Δρ_max = 0.25 e Å⁻³
2185 reflections	Δρ_min = −0.24 e Å⁻³
183 parameters

Special details top

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
F1	0.51229 (15)	0.68729 (6)	0.18505 (12)	0.0482 (3)
F2	0.78938 (15)	0.68491 (7)	0.24060 (12)	0.0473 (3)
F3	0.65809 (15)	0.58843 (5)	0.16378 (11)	0.0372 (3)
O1	0.36787 (14)	0.56226 (6)	0.71364 (11)	0.0222 (3)
O2	0.02826 (15)	0.51556 (7)	0.32441 (12)	0.0296 (3)
H2	−0.0560	0.4964	0.3661	0.044*
N1	0.70823 (17)	0.64542 (7)	0.51151 (15)	0.0248 (3)
N2	0.62765 (17)	0.62190 (7)	0.63485 (14)	0.0228 (3)
N3	0.15547 (16)	0.53763 (7)	0.42921 (14)	0.0220 (3)
C1	0.6393 (2)	0.64718 (9)	0.24941 (18)	0.0242 (4)
C2	0.59492 (19)	0.62818 (8)	0.40404 (17)	0.0203 (3)
C3	0.43940 (19)	0.59357 (8)	0.45480 (16)	0.0184 (3)
C4	0.46821 (19)	0.59138 (8)	0.60477 (16)	0.0189 (3)
C5	0.26932 (19)	0.61152 (8)	0.79966 (16)	0.0190 (3)
C6	0.1903 (2)	0.58217 (9)	0.92258 (16)	0.0217 (3)
H6	0.2044	0.5329	0.9455	0.026*
C7	0.0894 (2)	0.62741 (9)	1.01145 (16)	0.0242 (4)
H7	0.0346	0.6083	1.0941	0.029*
C8	0.0696 (2)	0.70110 (9)	0.97772 (17)	0.0237 (4)
H8	0.0027	0.7314	1.0378	0.028*
C9	0.1506 (2)	0.72911 (8)	0.85367 (18)	0.0244 (4)
H9	0.1377	0.7784	0.8309	0.029*
C10	0.2506 (2)	0.68442 (8)	0.76298 (17)	0.0216 (3)
H10	0.3040	0.7032	0.6793	0.026*
C11	0.2899 (2)	0.56673 (8)	0.36830 (16)	0.0201 (3)
H11	0.2922	0.5709	0.2665	0.024*
C12	0.7152 (2)	0.62954 (10)	0.77800 (19)	0.0334 (4)
H12A	0.6683	0.6715	0.8278	0.050*
H12B	0.8407	0.6356	0.7646	0.050*
H12C	0.6940	0.5865	0.8356	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0497 (7)	0.0564 (7)	0.0389 (6)	0.0268 (6)	0.0204 (5)	0.0248 (5)
F2	0.0449 (7)	0.0558 (7)	0.0417 (7)	−0.0275 (5)	0.0218 (5)	−0.0041 (5)
F3	0.0598 (7)	0.0258 (5)	0.0262 (5)	0.0001 (5)	0.0137 (5)	−0.0028 (4)
O1	0.0292 (6)	0.0187 (5)	0.0188 (6)	0.0001 (4)	0.0072 (5)	0.0010 (4)
O2	0.0249 (6)	0.0424 (7)	0.0216 (6)	−0.0154 (5)	−0.0038 (5)	0.0028 (5)
N1	0.0202 (7)	0.0250 (7)	0.0294 (7)	−0.0026 (5)	0.0054 (6)	−0.0023 (6)
N2	0.0210 (7)	0.0247 (7)	0.0227 (7)	−0.0007 (5)	0.0001 (5)	−0.0020 (5)
N3	0.0208 (7)	0.0241 (7)	0.0210 (7)	−0.0045 (5)	−0.0018 (5)	0.0003 (5)
C1	0.0220 (8)	0.0214 (8)	0.0293 (8)	−0.0004 (6)	0.0094 (7)	0.0001 (7)
C2	0.0186 (7)	0.0174 (7)	0.0251 (8)	0.0001 (6)	0.0059 (6)	−0.0011 (6)
C3	0.0184 (7)	0.0171 (7)	0.0196 (8)	0.0006 (6)	0.0046 (6)	0.0006 (6)
C4	0.0196 (7)	0.0169 (7)	0.0204 (8)	−0.0005 (6)	0.0033 (6)	0.0001 (6)
C5	0.0187 (7)	0.0222 (8)	0.0162 (7)	−0.0012 (6)	−0.0012 (6)	−0.0027 (6)
C6	0.0238 (8)	0.0228 (8)	0.0186 (8)	−0.0015 (6)	−0.0007 (6)	0.0035 (6)
C7	0.0223 (8)	0.0346 (9)	0.0158 (7)	−0.0019 (7)	0.0016 (6)	0.0022 (7)
C8	0.0204 (8)	0.0313 (9)	0.0194 (8)	0.0002 (6)	0.0008 (6)	−0.0061 (7)
C9	0.0260 (8)	0.0199 (8)	0.0274 (9)	−0.0018 (6)	0.0011 (7)	−0.0007 (6)
C10	0.0239 (8)	0.0227 (8)	0.0183 (8)	−0.0033 (6)	0.0026 (6)	0.0021 (6)
C11	0.0226 (8)	0.0211 (7)	0.0167 (7)	−0.0022 (6)	0.0028 (6)	0.0016 (6)
C12	0.0325 (9)	0.0381 (10)	0.0295 (9)	−0.0027 (8)	−0.0106 (7)	−0.0037 (8)

Geometric parameters (Å, º) top

F1—C1	1.3350 (19)	C5—C6	1.381 (2)
F2—C1	1.3260 (19)	C5—C10	1.381 (2)
F3—C1	1.3354 (19)	C6—C7	1.388 (2)
O1—C4	1.3601 (18)	C6—H6	0.9300
O1—C5	1.4089 (18)	C7—C8	1.389 (2)
O2—N3	1.4034 (17)	C7—H7	0.9300
O2—H2	0.8200	C8—C9	1.386 (2)
N1—C2	1.329 (2)	C8—H8	0.9300
N1—N2	1.3512 (19)	C9—C10	1.388 (2)
N2—C4	1.348 (2)	C9—H9	0.9300
N2—C12	1.460 (2)	C10—H10	0.9300
N3—C11	1.274 (2)	C11—H11	0.9300
C1—C2	1.491 (2)	C12—H12A	0.9600
C2—C3	1.412 (2)	C12—H12B	0.9600
C3—C4	1.380 (2)	C12—H12C	0.9600
C3—C11	1.452 (2)

C4—O1—C5	116.97 (11)	C5—C6—C7	118.88 (14)
N3—O2—H2	109.5	C5—C6—H6	120.6
C2—N1—N2	104.25 (12)	C7—C6—H6	120.6
C4—N2—N1	111.62 (13)	C6—C7—C8	120.46 (14)
C4—N2—C12	127.78 (14)	C6—C7—H7	119.8
N1—N2—C12	120.58 (13)	C8—C7—H7	119.8
C11—N3—O2	111.28 (12)	C9—C8—C7	119.43 (15)
F2—C1—F1	107.08 (14)	C9—C8—H8	120.3
F2—C1—F3	106.74 (13)	C7—C8—H8	120.3
F1—C1—F3	105.38 (14)	C8—C9—C10	120.79 (15)
F2—C1—C2	112.16 (14)	C8—C9—H9	119.6
F1—C1—C2	112.09 (13)	C10—C9—H9	119.6
F3—C1—C2	112.92 (13)	C5—C10—C9	118.60 (14)
N1—C2—C3	113.14 (14)	C5—C10—H10	120.7
N1—C2—C1	119.44 (13)	C9—C10—H10	120.7
C3—C2—C1	127.41 (14)	N3—C11—C3	121.26 (14)
C4—C3—C2	102.36 (13)	N3—C11—H11	119.4
C4—C3—C11	129.75 (14)	C3—C11—H11	119.4
C2—C3—C11	127.89 (14)	N2—C12—H12A	109.5
N2—C4—O1	120.87 (13)	N2—C12—H12B	109.5
N2—C4—C3	108.62 (13)	H12A—C12—H12B	109.5
O1—C4—C3	130.46 (13)	N2—C12—H12C	109.5
C6—C5—C10	121.83 (14)	H12A—C12—H12C	109.5
C6—C5—O1	115.79 (13)	H12B—C12—H12C	109.5
C10—C5—O1	122.38 (13)

C2—N1—N2—C4	−0.42 (16)	C5—O1—C4—C3	−103.49 (18)
C2—N1—N2—C12	178.30 (14)	C2—C3—C4—N2	−0.38 (16)
N2—N1—C2—C3	0.17 (17)	C11—C3—C4—N2	178.89 (15)
N2—N1—C2—C1	179.17 (13)	C2—C3—C4—O1	−177.58 (14)
F2—C1—C2—N1	−4.1 (2)	C11—C3—C4—O1	1.7 (3)
F1—C1—C2—N1	−124.64 (15)	C4—O1—C5—C6	−170.60 (13)
F3—C1—C2—N1	116.52 (16)	C4—O1—C5—C10	10.2 (2)
F2—C1—C2—C3	174.70 (14)	C10—C5—C6—C7	0.0 (2)
F1—C1—C2—C3	54.2 (2)	O1—C5—C6—C7	−179.25 (12)
F3—C1—C2—C3	−64.6 (2)	C5—C6—C7—C8	−0.5 (2)
N1—C2—C3—C4	0.13 (17)	C6—C7—C8—C9	0.5 (2)
C1—C2—C3—C4	−178.78 (15)	C7—C8—C9—C10	0.1 (2)
N1—C2—C3—C11	−179.16 (14)	C6—C5—C10—C9	0.6 (2)
C1—C2—C3—C11	1.9 (3)	O1—C5—C10—C9	179.76 (13)
N1—N2—C4—O1	178.05 (12)	C8—C9—C10—C5	−0.6 (2)
C12—N2—C4—O1	−0.6 (2)	O2—N3—C11—C3	−179.74 (13)
N1—N2—C4—C3	0.52 (17)	C4—C3—C11—N3	2.3 (3)
C12—N2—C4—C3	−178.08 (15)	C2—C3—C11—N3	−178.62 (15)
C5—O1—C4—N2	79.59 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···F1ⁱ	0.93	2.54	3.147 (2)	123
O2—H2···N3ⁱⁱ	0.82	2.11	2.819 (2)	145

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀F₃N₃O₂
M_r	285.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	7.5221 (15), 18.282 (4), 9.1002 (18)
β (°)	90.58 (3)
V (Å³)	1251.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.24 × 0.16 × 0.14

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.968, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	7050, 2185, 1910
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.101, 1.06
No. of reflections	2185
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.24

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···F1ⁱ	0.93	2.54	3.147 (2)	123
O2—H2···N3ⁱⁱ	0.82	2.11	2.819 (2)	145

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, −y+1, −z+1.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (NNSFC) (grant No. 20772068), the Science and Technology Projects Fund of Nantong City (grant Nos. K2010016, AS2010005), the Science Foundation of Nantong University (grant Nos. 09Z010, 09C001) and the Scientific Research Foundation for Talent Introduction of Nantong University.

References

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