5-(3-Chloro­phen­ylsulfan­yl)-1-methyl-3-trifluoro­methyl-1H-pyrazole-4-carbaldehyde O-[(2-chloro-1,3-thia­zol-5-yl)meth­yl]oxime

Abstract

In the title compound, C₁₆H₁₁Cl₂F₃N₄OS₂, the benzene ring and the thia­zole ring make dihedral angles of 83.2 (3) and 78.3 (3)°, respectively, with the pyrazole ring. The crystal packing shows S⋯N contacts of 3.309 (2) Å.

Related literature

For the bioactivity of pyrazole oxime derivatives, see: Takao et al. (1994 ▶); Watanabe et al. (2001 ▶). For the biological activity of thia­zole derivatives, see: Fahmy & Bekhit (2002 ▶); Sidoova et al. (1999 ▶); Zhang et al. (2000 ▶).

Experimental

Crystal data

• C₁₆H₁₁Cl₂F₃N₄OS₂

• M _r = 467.31

• Monoclinic,

• a = 12.328 (3) Å

• b = 12.787 (3) Å

• c = 13.139 (3) Å

• β = 110.16 (3)°

• V = 1944.3 (9) ų

• Z = 4

• Mo Kα radiation

• μ = 0.59 mm⁻¹

• T = 113 K

• 0.20 × 0.16 × 0.10 mm

Data collection

• Rigaku Saturn diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ▶) T _min = 0.891, T _max = 0.943

• 9881 measured reflections

• 3309 independent reflections

• 2725 reflections with I > 2σ(I)

• R _int = 0.116

Refinement

• R[F ² > 2σ(F ²)] = 0.088

• wR(F ²) = 0.273

• S = 1.10

• 3309 reflections

• 254 parameters

• H-atom parameters constrained

• Δρ_max = 0.81 e Å⁻³

• Δρ_min = −0.94 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681105358X/aa2035Isup3.cml

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

supplementary crystallographic information

Comment

Recently, pyrazole oximes are reported to possess diverse biological activities, such as fungicidal, insecticidal, and acaricidal activities (Takao et al., 1994; Watanabe et al., 2001). On the other hand, many thiazole derivatives have been found to show insecticidal, herbicidal, and anticancer activities (Sidoova et al., 1999; Zhang et al., 2000; Fahmy & Bekhit, 2002). In search of novel pyrazole oxime derivatives with good bioactivities, we have sought to synthesize new pyrazole oxime ethers containing thiazole units. We report here the crystal structure of the target compound, (I). It contains three planes, the pyrazole ring (C2/C3/C4/N1/N2), the substituted phenyl ring (C6/C7/C8/C9/C10/C11) and the thiazole ring (C15/C14/S2/C16/N4) (Fig. 1). The dihedral angles between the the phenyl ring and the pyrazole ring and between the thiazole ring and the pyrazole ring are 83.2 (3)° and 78.3 (3)°, respectively. The crystal structure of (I) is stabilized by S···N contacts.

Experimental

To a violently stirred solution of 1-methyl-3-trifluoromethyl-5- (3-chlorophenylthio)-1H-pyrazole-4-carbaldehyde oxime (3 mmol) and potassium carbonate (9 mmol) in 20 ml of anhydrous N,N-dimethylformamide, was added dropwise a solution of 2-chloro-5-chloromethylthiazole (3.6 mmol) in 10 ml of anhydrous N,N-dimethylformamide. Then, to the above mixture was added a catalytic amount of caesium chloride at room temperature. The resulting solution was heated to 373 K for 6 h. After cooling to room temperature, the mixture was poured into water (200 ml) and extracted with ethyl acetate (3 × 50 ml). The organic layer was washed with 10% sodium carbonate solution (3 × 30 ml) and dried over anhydrous magnesium sulfate. After removal of the solvent, the residue was separated by column chromatography on silica gel using a mixture of petroleum ether/ethyl acetate to obtain colourless crystals.

Refinement

Although all H atoms were visible in difference maps, they were placed in geometrically calculated positions and included in the final refinement in the riding-model approximation with C—H distances of 0.93–0.97 ° A, and U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

View of the title compound (I), with displacement ellipsoids drawn at the 30% probability level.

Crystal data

C16H11Cl2F3N4OS2	F(000) = 944
Mr = 467.31	Dx = 1.597 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5433 reflections
a = 12.328 (3) Å	θ = 1.6–27.2°
b = 12.787 (3) Å	µ = 0.59 mm−1
c = 13.139 (3) Å	T = 113 K
β = 110.16 (3)°	Prism, colourless
V = 1944.3 (9) Å3	0.20 × 0.16 × 0.10 mm
Z = 4

Data collection

Rigaku Saturn diffractometer	3309 independent reflections
Radiation source: rotating anode	2725 reflections with I > 2σ(I)
confocal	Rint = 0.116
ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	h = −11→14
Tmin = 0.891, Tmax = 0.943	k = −15→14
9881 measured reflections	l = −15→15

Refinement

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)] = 0.088	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.273	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.2P)2] where P = (Fo2 + 2Fc2)/3
3309 reflections	(Δ/σ)max = 0.001
254 parameters	Δρmax = 0.81 e Å−3
0 restraints	Δρmin = −0.94 e Å−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.01343 (10)	0.94499 (10)	0.66778 (11)	0.0519 (5)
Cl2	0.57227 (10)	0.80206 (10)	0.00569 (10)	0.0483 (4)
S1	0.36532 (9)	1.11017 (8)	0.55348 (9)	0.0348 (4)
S2	0.38132 (9)	0.80301 (8)	0.09658 (8)	0.0334 (4)
F1	0.2428 (2)	0.69627 (18)	0.3650 (2)	0.0403 (7)
F2	0.3861 (2)	0.62954 (18)	0.49260 (18)	0.0396 (7)
F3	0.4134 (2)	0.70073 (18)	0.3550 (2)	0.0388 (7)
O1	0.1746 (3)	0.9511 (2)	0.1630 (2)	0.0351 (7)
N1	0.4428 (3)	0.9119 (3)	0.6202 (2)	0.0280 (7)
N2	0.4393 (3)	0.8114 (2)	0.5871 (3)	0.0293 (8)
N3	0.2447 (3)	0.8956 (2)	0.2545 (3)	0.0312 (8)
N4	0.3842 (3)	0.9182 (3)	−0.0643 (3)	0.0402 (9)
C1	0.3548 (3)	0.7100 (3)	0.4235 (3)	0.0305 (9)
C2	0.3752 (3)	0.8122 (3)	0.4828 (3)	0.0283 (9)
C3	0.3354 (3)	0.9140 (3)	0.4454 (3)	0.0279 (8)
C4	0.3791 (3)	0.9760 (3)	0.5370 (3)	0.0285 (8)
C5	0.5030 (4)	0.9391 (3)	0.7338 (3)	0.0381 (10)
H5A	0.4487	0.9410	0.7714	0.057*
H5B	0.5386	1.0065	0.7379	0.057*
H5C	0.5613	0.8876	0.7666	0.057*
C6	0.2689 (3)	1.1125 (3)	0.6278 (3)	0.0310 (9)
C7	0.2734 (4)	1.2006 (3)	0.6906 (3)	0.0348 (10)
H7	0.3280	1.2526	0.6967	0.042*
C8	0.1934 (4)	1.2099 (3)	0.7451 (4)	0.0405 (11)
H8	0.1950	1.2690	0.7869	0.049*
C9	0.1125 (4)	1.1326 (3)	0.7376 (3)	0.0397 (10)
H9	0.0596	1.1389	0.7734	0.048*
C10	0.1127 (4)	1.0458 (3)	0.6753 (3)	0.0345 (9)
C11	0.1877 (3)	1.0346 (3)	0.6185 (3)	0.0328 (9)
H11	0.1839	0.9763	0.5750	0.039*
C12	0.2648 (3)	0.9524 (3)	0.3388 (3)	0.0308 (9)
H12	0.2339	1.0195	0.3321	0.037*
C13	0.1586 (4)	0.8867 (3)	0.0688 (3)	0.0351 (10)
H13A	0.0938	0.9134	0.0089	0.042*
H13B	0.1397	0.8161	0.0841	0.042*
C14	0.2639 (3)	0.8834 (3)	0.0357 (3)	0.0302 (9)
C15	0.2824 (4)	0.9380 (3)	−0.0462 (3)	0.0360 (10)
H15	0.2288	0.9862	−0.0877	0.043*
C16	0.4424 (4)	0.8484 (3)	0.0046 (3)	0.0355 (10)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0347 (7)	0.0614 (8)	0.0707 (9)	−0.0063 (5)	0.0322 (6)	−0.0026 (5)
Cl2	0.0299 (7)	0.0728 (9)	0.0460 (7)	0.0030 (5)	0.0179 (5)	−0.0001 (5)
S1	0.0347 (7)	0.0345 (6)	0.0437 (7)	−0.0039 (4)	0.0244 (5)	−0.0030 (4)
S2	0.0270 (7)	0.0436 (7)	0.0312 (7)	0.0031 (4)	0.0119 (5)	0.0028 (4)
F1	0.0242 (13)	0.0447 (14)	0.0503 (15)	−0.0077 (9)	0.0109 (11)	−0.0058 (10)
F2	0.0461 (16)	0.0323 (12)	0.0411 (14)	0.0024 (10)	0.0161 (12)	0.0052 (9)
F3	0.0392 (15)	0.0408 (13)	0.0442 (14)	−0.0027 (10)	0.0244 (12)	−0.0076 (10)
O1	0.0342 (16)	0.0420 (15)	0.0284 (14)	0.0115 (11)	0.0100 (12)	0.0036 (11)
N1	0.0197 (16)	0.0392 (17)	0.0297 (17)	−0.0036 (13)	0.0143 (13)	−0.0025 (13)
N2	0.0219 (17)	0.0339 (17)	0.0336 (18)	−0.0021 (12)	0.0115 (14)	−0.0001 (13)
N3	0.0263 (18)	0.0370 (18)	0.0319 (17)	0.0058 (13)	0.0120 (14)	0.0054 (13)
N4	0.036 (2)	0.054 (2)	0.0329 (19)	−0.0050 (17)	0.0147 (16)	0.0029 (17)
C1	0.022 (2)	0.040 (2)	0.033 (2)	0.0003 (15)	0.0145 (16)	0.0024 (16)
C2	0.0200 (19)	0.037 (2)	0.032 (2)	−0.0028 (14)	0.0142 (16)	−0.0006 (15)
C3	0.0203 (19)	0.0370 (19)	0.032 (2)	−0.0006 (14)	0.0160 (16)	0.0011 (15)
C4	0.0191 (18)	0.040 (2)	0.034 (2)	−0.0026 (15)	0.0190 (16)	−0.0001 (15)
C5	0.031 (2)	0.048 (2)	0.035 (2)	−0.0055 (17)	0.0110 (18)	−0.0068 (18)
C6	0.026 (2)	0.040 (2)	0.0281 (19)	0.0018 (15)	0.0111 (16)	0.0017 (15)
C7	0.036 (2)	0.035 (2)	0.036 (2)	0.0047 (15)	0.016 (2)	0.0016 (15)
C8	0.042 (3)	0.047 (2)	0.036 (2)	0.0157 (19)	0.019 (2)	−0.0039 (18)
C9	0.033 (2)	0.056 (3)	0.035 (2)	0.0158 (19)	0.0181 (19)	0.0011 (19)
C10	0.024 (2)	0.046 (2)	0.036 (2)	0.0040 (16)	0.0134 (17)	0.0046 (17)
C11	0.026 (2)	0.041 (2)	0.033 (2)	0.0066 (16)	0.0125 (17)	0.0007 (16)
C12	0.025 (2)	0.036 (2)	0.035 (2)	0.0039 (15)	0.0158 (17)	0.0010 (15)
C13	0.029 (2)	0.047 (2)	0.029 (2)	0.0040 (16)	0.0098 (17)	0.0009 (16)
C14	0.0233 (19)	0.038 (2)	0.0286 (19)	0.0009 (15)	0.0077 (16)	−0.0017 (15)
C15	0.033 (2)	0.040 (2)	0.034 (2)	0.0066 (16)	0.0105 (18)	0.0056 (16)
C16	0.030 (2)	0.047 (2)	0.031 (2)	−0.0041 (17)	0.0120 (17)	−0.0030 (17)

Geometric parameters (Å, °)

Cl1—C10	1.756 (4)	C3—C12	1.456 (5)
Cl2—C16	1.703 (4)	C5—H5A	0.9600
S1—C4	1.744 (4)	C5—H5B	0.9600
S1—C6	1.780 (4)	C5—H5C	0.9600
S2—C16	1.729 (4)	C6—C7	1.386 (6)
S2—C14	1.730 (4)	C6—C11	1.387 (6)
F1—C1	1.341 (5)	C7—C8	1.409 (6)
F2—C1	1.338 (5)	C7—H7	0.9300
F3—C1	1.339 (5)	C8—C9	1.383 (7)
O1—N3	1.407 (4)	C8—H8	0.9300
O1—C13	1.442 (5)	C9—C10	1.380 (6)
N1—N2	1.352 (5)	C9—H9	0.9300
N1—C4	1.376 (5)	C10—C11	1.382 (6)
N1—C5	1.461 (5)	C11—H11	0.9300
N2—C2	1.325 (5)	C12—H12	0.9300
N3—C12	1.275 (5)	C13—C14	1.505 (6)
N4—C16	1.298 (6)	C13—H13A	0.9700
N4—C15	1.379 (6)	C13—H13B	0.9700
C1—C2	1.497 (5)	C14—C15	1.366 (6)
C2—C3	1.418 (5)	C15—H15	0.9300
C3—C4	1.386 (5)
C4—S1—C6	101.37 (18)	C6—C7—C8	118.7 (4)
C16—S2—C14	88.5 (2)	C6—C7—H7	120.7
N3—O1—C13	107.9 (3)	C8—C7—H7	120.7
N2—N1—C4	111.4 (3)	C9—C8—C7	121.1 (4)
N2—N1—C5	120.2 (3)	C9—C8—H8	119.4
C4—N1—C5	128.3 (3)	C7—C8—H8	119.4
C2—N2—N1	105.5 (3)	C10—C9—C8	117.9 (4)
C12—N3—O1	109.5 (3)	C10—C9—H9	121.0
C16—N4—C15	108.8 (4)	C8—C9—H9	121.0
F2—C1—F3	107.0 (3)	C9—C10—C11	122.8 (4)
F2—C1—F1	106.7 (3)	C9—C10—Cl1	118.7 (3)
F3—C1—F1	106.9 (3)	C11—C10—Cl1	118.5 (3)
F2—C1—C2	111.1 (3)	C10—C11—C6	118.4 (4)
F3—C1—C2	113.3 (3)	C10—C11—H11	120.8
F1—C1—C2	111.6 (3)	C6—C11—H11	120.8
N2—C2—C3	112.2 (3)	N3—C12—C3	121.1 (4)
N2—C2—C1	117.7 (3)	N3—C12—H12	119.5
C3—C2—C1	130.1 (4)	C3—C12—H12	119.5
C4—C3—C2	103.9 (3)	O1—C13—C14	112.8 (3)
C4—C3—C12	124.5 (4)	O1—C13—H13A	109.0
C2—C3—C12	131.6 (3)	C14—C13—H13A	109.0
N1—C4—C3	107.0 (3)	O1—C13—H13B	109.0
N1—C4—S1	122.7 (3)	C14—C13—H13B	109.0
C3—C4—S1	130.2 (3)	H13A—C13—H13B	107.8
N1—C5—H5A	109.5	C15—C14—C13	127.5 (4)
N1—C5—H5B	109.5	C15—C14—S2	109.1 (3)
H5A—C5—H5B	109.5	C13—C14—S2	123.4 (3)
N1—C5—H5C	109.5	C14—C15—N4	116.8 (4)
H5A—C5—H5C	109.5	C14—C15—H15	121.6
H5B—C5—H5C	109.5	N4—C15—H15	121.6
C7—C6—C11	121.0 (4)	N4—C16—Cl2	122.5 (3)
C7—C6—S1	116.3 (3)	N4—C16—S2	116.7 (3)
C11—C6—S1	122.5 (3)	Cl2—C16—S2	120.8 (3)
C4—N1—N2—C2	1.0 (4)	C4—S1—C6—C11	−28.8 (4)
C5—N1—N2—C2	177.4 (3)	C11—C6—C7—C8	0.0 (6)
C13—O1—N3—C12	177.1 (3)	S1—C6—C7—C8	175.6 (3)
N1—N2—C2—C3	0.1 (4)	C6—C7—C8—C9	0.7 (6)
N1—N2—C2—C1	−179.5 (3)	C7—C8—C9—C10	0.2 (6)
F2—C1—C2—N2	13.1 (5)	C8—C9—C10—C11	−1.8 (6)
F3—C1—C2—N2	−107.4 (4)	C8—C9—C10—Cl1	178.2 (3)
F1—C1—C2—N2	131.9 (4)	C9—C10—C11—C6	2.4 (6)
F2—C1—C2—C3	−166.4 (4)	Cl1—C10—C11—C6	−177.6 (3)
F3—C1—C2—C3	73.2 (5)	C7—C6—C11—C10	−1.4 (6)
F1—C1—C2—C3	−47.5 (5)	S1—C6—C11—C10	−176.8 (3)
N2—C2—C3—C4	−1.1 (4)	O1—N3—C12—C3	179.8 (3)
C1—C2—C3—C4	178.4 (4)	C4—C3—C12—N3	167.3 (4)
N2—C2—C3—C12	179.3 (4)	C2—C3—C12—N3	−13.1 (7)
C1—C2—C3—C12	−1.3 (7)	N3—O1—C13—C14	−75.3 (4)
N2—N1—C4—C3	−1.7 (4)	O1—C13—C14—C15	−100.8 (5)
C5—N1—C4—C3	−177.7 (4)	O1—C13—C14—S2	81.4 (4)
N2—N1—C4—S1	179.5 (3)	C16—S2—C14—C15	−1.1 (3)
C5—N1—C4—S1	3.5 (5)	C16—S2—C14—C13	177.0 (4)
C2—C3—C4—N1	1.6 (4)	C13—C14—C15—N4	−177.1 (4)
C12—C3—C4—N1	−178.7 (3)	S2—C14—C15—N4	0.9 (5)
C2—C3—C4—S1	−179.7 (3)	C16—N4—C15—C14	−0.1 (5)
C12—C3—C4—S1	0.0 (6)	C15—N4—C16—Cl2	178.8 (3)
C6—S1—C4—N1	−74.0 (3)	C15—N4—C16—S2	−0.9 (5)
C6—S1—C4—C3	107.5 (4)	C14—S2—C16—N4	1.2 (3)
C4—S1—C6—C7	155.6 (3)	C14—S2—C16—Cl2	−178.5 (3)