Ethyl 2-[5-(4-chloro-phen-yl)-1-(4-fluoro-phen-yl)-1H-pyrazol-3-yl]-4-methyl-thia-zole-5-carboxyl-ate.

In the title compound, C(22)H(17)ClFN(3)O(2)S, the pyrazole ring is approximately planar with a maximum deviation of 0.001 (4) Å and makes dihedral angles of 4.95 (19), 35.78 (18) and 54.73 (18)° with the thia-zole, fluoro-benzene and chloro-benzene rings, respectively. In the crystal, inter-molecular C-H⋯O hydrogen bonds link the mol-ecules into chains along the a axis.

Related literature

For background to pyrazole derivatives and their anti­microbial activity, see: Ragavan et al. (2009 ▶, 2010 ▶). For bond-length data, see: Allen et al. (1987 ▶). For a related structure, see: Loh et al. (2010 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C22H17ClFN3O2S

M = 441.90

Monoclinic,

a = 12.0296 (5) Å

b = 19.4428 (6) Å

c = 9.5847 (3) Å

β = 112.922 (1)°

V = 2064.74 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.32 mm−1

T = 100 K

0.42 × 0.17 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS, Bruker, 2009 ▶) T min = 0.878, T max = 0.976

30630 measured reflections

4697 independent reflections

3944 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.163

S = 1.24

4697 reflections

273 parameters

H-atom parameters constrained

Δρmax = 0.63 e Å−3

Δρmin = −0.53 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810042066/fj2354sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810042066/fj2354Isup2.hkl

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

C22H17ClFN3O2S	F(000) = 912
Mr = 441.90	Dx = 1.422 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9879 reflections
a = 12.0296 (5) Å	θ = 2.8–32.9°
b = 19.4428 (6) Å	µ = 0.32 mm−1
c = 9.5847 (3) Å	T = 100 K
β = 112.922 (1)°	Plate, colourless
V = 2064.74 (12) Å3	0.42 × 0.17 × 0.08 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	4697 independent reflections
Radiation source: fine-focus sealed tube	3944 reflections with I > 2σ(I)
graphite	Rint = 0.043
φ and ω scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS, Bruker, 2009)	h = −15→15
Tmin = 0.878, Tmax = 0.976	k = −25→25
30630 measured reflections	l = −12→12

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.163	H-atom parameters constrained
S = 1.24	w = 1/[σ2(Fo2) + (0.P)2 + 9.3055P] where P = (Fo2 + 2Fc2)/3
4697 reflections	(Δ/σ)max < 0.001
273 parameters	Δρmax = 0.63 e Å−3
0 restraints	Δρmin = −0.53 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

	x	y	z	Uiso*/Ueq
S1	0.28859 (8)	0.28472 (4)	−0.01128 (10)	0.0162 (2)
Cl1	−0.24355 (9)	−0.04920 (5)	0.40468 (12)	0.0288 (2)
F1	−0.2939 (2)	0.38188 (13)	0.2896 (3)	0.0373 (6)
O1	0.4449 (2)	0.36177 (13)	−0.1138 (3)	0.0239 (6)
O2	0.5434 (2)	0.27417 (14)	−0.1712 (3)	0.0247 (6)
N1	0.0936 (3)	0.24138 (15)	0.0961 (3)	0.0161 (6)
N2	0.0143 (3)	0.21207 (15)	0.1472 (3)	0.0154 (6)
N3	0.3202 (3)	0.15335 (15)	0.0001 (4)	0.0176 (6)
C1	0.0322 (3)	0.14214 (17)	0.1675 (4)	0.0160 (7)
C2	0.1269 (3)	0.12630 (18)	0.1269 (4)	0.0165 (7)
H2A	0.1608	0.0832	0.1279	0.020*
C3	0.1616 (3)	0.18936 (18)	0.0837 (4)	0.0164 (7)
C4	0.2558 (3)	0.20259 (17)	0.0272 (4)	0.0155 (7)
C5	0.4011 (3)	0.18060 (18)	−0.0546 (4)	0.0178 (7)
C6	0.3963 (3)	0.25092 (18)	−0.0694 (4)	0.0165 (7)
C7	0.4701 (3)	0.29491 (19)	−0.1238 (4)	0.0185 (7)
C8	0.5145 (4)	0.4118 (2)	−0.1592 (5)	0.0281 (9)
H8A	0.5329	0.3938	−0.2422	0.034*
H8B	0.5898	0.4220	−0.0750	0.034*
C9	0.4385 (4)	0.4758 (2)	−0.2080 (5)	0.0326 (10)
H9A	0.4861	0.5124	−0.2229	0.049*
H9B	0.4099	0.4887	−0.1310	0.049*
H9C	0.3708	0.4669	−0.3010	0.049*
C10	0.4855 (4)	0.1330 (2)	−0.0880 (5)	0.0257 (9)
H10A	0.4783	0.1399	−0.1903	0.039*
H10B	0.4654	0.0863	−0.0754	0.039*
H10C	0.5669	0.1424	−0.0196	0.039*
C11	−0.0686 (3)	0.25574 (18)	0.1786 (4)	0.0150 (7)
C12	−0.0298 (3)	0.32104 (18)	0.2356 (4)	0.0179 (7)
H12A	0.0474	0.3358	0.2498	0.021*
C13	−0.1070 (3)	0.36415 (19)	0.2714 (4)	0.0207 (8)
H13A	−0.0829	0.4083	0.3082	0.025*
C14	−0.2197 (4)	0.3401 (2)	0.2510 (5)	0.0247 (8)
C15	−0.2614 (3)	0.2759 (2)	0.1924 (5)	0.0242 (8)
H15A	−0.3383	0.2613	0.1796	0.029*
C16	−0.1848 (3)	0.2336 (2)	0.1528 (4)	0.0215 (8)
H16A	−0.2113	0.1908	0.1093	0.026*
C17	−0.0370 (3)	0.09629 (17)	0.2271 (4)	0.0162 (7)
C18	−0.0471 (3)	0.10914 (19)	0.3647 (4)	0.0207 (8)
H18A	−0.0105	0.1478	0.4208	0.025*
C19	−0.1115 (3)	0.06460 (19)	0.4186 (5)	0.0229 (8)
H19A	−0.1185	0.0732	0.5103	0.027*
C20	−0.1653 (3)	0.00709 (18)	0.3334 (5)	0.0205 (8)
C21	−0.1571 (3)	−0.00729 (18)	0.1970 (5)	0.0217 (8)
H21A	−0.1939	−0.0461	0.1416	0.026*
C22	−0.0923 (3)	0.03780 (18)	0.1440 (4)	0.0204 (8)
H22A	−0.0858	0.0289	0.0521	0.025*

	U11	U22	U33	U12	U13	U23
S1	0.0197 (4)	0.0132 (4)	0.0191 (5)	0.0005 (3)	0.0115 (3)	−0.0001 (3)
Cl1	0.0279 (5)	0.0246 (5)	0.0372 (6)	−0.0057 (4)	0.0161 (4)	0.0090 (4)
F1	0.0383 (14)	0.0349 (14)	0.0523 (18)	0.0144 (11)	0.0324 (13)	0.0036 (12)
O1	0.0305 (14)	0.0161 (12)	0.0328 (16)	−0.0035 (11)	0.0209 (13)	0.0009 (11)
O2	0.0246 (14)	0.0259 (14)	0.0306 (16)	−0.0008 (11)	0.0184 (12)	0.0002 (12)
N1	0.0176 (14)	0.0160 (14)	0.0180 (16)	−0.0010 (11)	0.0104 (12)	0.0007 (12)
N2	0.0165 (14)	0.0137 (14)	0.0184 (16)	−0.0008 (11)	0.0093 (12)	−0.0001 (11)
N3	0.0198 (14)	0.0151 (14)	0.0198 (17)	−0.0012 (11)	0.0096 (12)	−0.0017 (12)
C1	0.0181 (16)	0.0141 (16)	0.0151 (18)	−0.0028 (13)	0.0058 (13)	−0.0019 (13)
C2	0.0207 (17)	0.0148 (16)	0.0153 (18)	−0.0004 (13)	0.0085 (14)	−0.0014 (13)
C3	0.0163 (16)	0.0154 (16)	0.0194 (19)	−0.0008 (12)	0.0088 (14)	−0.0010 (13)
C4	0.0168 (16)	0.0143 (16)	0.0160 (18)	−0.0014 (12)	0.0069 (13)	−0.0002 (13)
C5	0.0189 (17)	0.0177 (16)	0.0185 (19)	−0.0005 (13)	0.0090 (14)	−0.0028 (14)
C6	0.0178 (16)	0.0192 (17)	0.0145 (18)	−0.0005 (13)	0.0086 (14)	−0.0034 (13)
C7	0.0190 (17)	0.0208 (17)	0.0160 (19)	−0.0027 (13)	0.0072 (14)	−0.0004 (14)
C8	0.031 (2)	0.0214 (19)	0.038 (3)	−0.0080 (16)	0.0197 (19)	0.0015 (17)
C9	0.034 (2)	0.022 (2)	0.040 (3)	−0.0068 (17)	0.013 (2)	0.0059 (18)
C10	0.0263 (19)	0.0199 (18)	0.038 (2)	0.0011 (15)	0.0207 (18)	−0.0050 (17)
C11	0.0191 (16)	0.0188 (16)	0.0097 (17)	0.0032 (13)	0.0084 (13)	0.0027 (13)
C12	0.0187 (17)	0.0179 (17)	0.0174 (19)	0.0013 (13)	0.0074 (14)	0.0022 (14)
C13	0.0302 (19)	0.0203 (17)	0.0136 (18)	0.0050 (15)	0.0105 (15)	0.0018 (14)
C14	0.0262 (19)	0.028 (2)	0.026 (2)	0.0118 (16)	0.0168 (17)	0.0062 (17)
C15	0.0183 (17)	0.030 (2)	0.027 (2)	0.0033 (15)	0.0113 (16)	0.0083 (17)
C16	0.0192 (17)	0.0217 (18)	0.024 (2)	−0.0005 (14)	0.0090 (15)	0.0037 (15)
C17	0.0179 (16)	0.0142 (16)	0.0179 (19)	0.0006 (13)	0.0084 (14)	0.0016 (13)
C18	0.0223 (18)	0.0159 (16)	0.024 (2)	−0.0039 (14)	0.0097 (15)	−0.0008 (14)
C19	0.0252 (19)	0.0219 (18)	0.026 (2)	−0.0018 (15)	0.0141 (16)	0.0015 (15)
C20	0.0195 (17)	0.0170 (17)	0.027 (2)	−0.0014 (13)	0.0115 (15)	0.0067 (15)
C21	0.0246 (18)	0.0139 (16)	0.026 (2)	−0.0033 (14)	0.0094 (16)	−0.0010 (15)
C22	0.0265 (19)	0.0164 (17)	0.021 (2)	−0.0020 (14)	0.0121 (16)	−0.0028 (14)

S1—C4	1.719 (3)	C9—H9B	0.9600
S1—C6	1.727 (3)	C9—H9C	0.9600
Cl1—C20	1.747 (4)	C10—H10A	0.9600
F1—C14	1.360 (4)	C10—H10B	0.9600
O1—C7	1.347 (4)	C10—H10C	0.9600
O1—C8	1.456 (4)	C11—C12	1.389 (5)
O2—C7	1.207 (4)	C11—C16	1.389 (5)
N1—C3	1.334 (4)	C12—C13	1.389 (5)
N1—N2	1.356 (4)	C12—H12A	0.9300
N2—C1	1.378 (4)	C13—C14	1.375 (5)
N2—C11	1.429 (4)	C13—H13A	0.9300
N3—C4	1.319 (4)	C14—C15	1.380 (6)
N3—C5	1.378 (4)	C15—C16	1.393 (5)
C1—C2	1.374 (5)	C15—H15A	0.9300
C1—C17	1.478 (5)	C16—H16A	0.9300
C2—C3	1.408 (5)	C17—C18	1.394 (5)
C2—H2A	0.9300	C17—C22	1.399 (5)
C3—C4	1.457 (5)	C18—C19	1.389 (5)
C5—C6	1.373 (5)	C18—H18A	0.9300
C5—C10	1.498 (5)	C19—C20	1.387 (5)
C6—C7	1.467 (5)	C19—H19A	0.9300
C8—C9	1.507 (6)	C20—C21	1.378 (6)
C8—H8A	0.9700	C21—C22	1.394 (5)
C8—H8B	0.9700	C21—H21A	0.9300
C9—H9A	0.9600	C22—H22A	0.9300
C4—S1—C6	88.81 (17)	C5—C10—H10B	109.5
C7—O1—C8	116.8 (3)	H10A—C10—H10B	109.5
C3—N1—N2	104.8 (3)	C5—C10—H10C	109.5
N1—N2—C1	111.8 (3)	H10A—C10—H10C	109.5
N1—N2—C11	118.3 (3)	H10B—C10—H10C	109.5
C1—N2—C11	129.8 (3)	C12—C11—C16	120.9 (3)
C4—N3—C5	110.6 (3)	C12—C11—N2	118.1 (3)
C2—C1—N2	106.4 (3)	C16—C11—N2	121.0 (3)
C2—C1—C17	128.9 (3)	C13—C12—C11	119.6 (3)
N2—C1—C17	124.7 (3)	C13—C12—H12A	120.2
C1—C2—C3	105.1 (3)	C11—C12—H12A	120.2
C1—C2—H2A	127.4	C14—C13—C12	118.5 (4)
C3—C2—H2A	127.4	C14—C13—H13A	120.8
N1—C3—C2	111.8 (3)	C12—C13—H13A	120.8
N1—C3—C4	119.4 (3)	F1—C14—C13	118.2 (4)
C2—C3—C4	128.7 (3)	F1—C14—C15	118.6 (4)
N3—C4—C3	123.1 (3)	C13—C14—C15	123.2 (3)
N3—C4—S1	115.5 (3)	C14—C15—C16	118.1 (3)
C3—C4—S1	121.4 (3)	C14—C15—H15A	120.9
C6—C5—N3	114.5 (3)	C16—C15—H15A	120.9
C6—C5—C10	126.7 (3)	C11—C16—C15	119.6 (4)
N3—C5—C10	118.8 (3)	C11—C16—H16A	120.2
C5—C6—C7	127.6 (3)	C15—C16—H16A	120.2
C5—C6—S1	110.6 (3)	C18—C17—C22	119.1 (3)
C7—C6—S1	121.8 (3)	C18—C17—C1	121.8 (3)
O2—C7—O1	124.5 (3)	C22—C17—C1	119.0 (3)
O2—C7—C6	124.8 (3)	C19—C18—C17	120.5 (3)
O1—C7—C6	110.7 (3)	C19—C18—H18A	119.8
O1—C8—C9	107.1 (3)	C17—C18—H18A	119.8
O1—C8—H8A	110.3	C20—C19—C18	118.9 (4)
C9—C8—H8A	110.3	C20—C19—H19A	120.6
O1—C8—H8B	110.3	C18—C19—H19A	120.6
C9—C8—H8B	110.3	C21—C20—C19	122.2 (3)
H8A—C8—H8B	108.6	C21—C20—Cl1	119.5 (3)
C8—C9—H9A	109.5	C19—C20—Cl1	118.3 (3)
C8—C9—H9B	109.5	C20—C21—C22	118.4 (3)
H9A—C9—H9B	109.5	C20—C21—H21A	120.8
C8—C9—H9C	109.5	C22—C21—H21A	120.8
H9A—C9—H9C	109.5	C21—C22—C17	120.9 (4)
H9B—C9—H9C	109.5	C21—C22—H22A	119.6
C5—C10—H10A	109.5	C17—C22—H22A	119.6
C3—N1—N2—C1	0.2 (4)	C5—C6—C7—O1	−176.2 (4)
C3—N1—N2—C11	177.3 (3)	S1—C6—C7—O1	2.9 (4)
N1—N2—C1—C2	−0.2 (4)	C7—O1—C8—C9	154.3 (4)
C11—N2—C1—C2	−176.9 (3)	N1—N2—C11—C12	−34.4 (5)
N1—N2—C1—C17	177.8 (3)	C1—N2—C11—C12	142.0 (4)
C11—N2—C1—C17	1.1 (6)	N1—N2—C11—C16	145.5 (3)
N2—C1—C2—C3	0.1 (4)	C1—N2—C11—C16	−38.0 (5)
C17—C1—C2—C3	−177.8 (4)	C16—C11—C12—C13	1.8 (5)
N2—N1—C3—C2	−0.1 (4)	N2—C11—C12—C13	−178.2 (3)
N2—N1—C3—C4	178.5 (3)	C11—C12—C13—C14	1.0 (5)
C1—C2—C3—N1	0.0 (4)	C12—C13—C14—F1	178.4 (3)
C1—C2—C3—C4	−178.5 (4)	C12—C13—C14—C15	−2.1 (6)
C5—N3—C4—C3	179.1 (3)	F1—C14—C15—C16	179.8 (3)
C5—N3—C4—S1	0.0 (4)	C13—C14—C15—C16	0.3 (6)
N1—C3—C4—N3	−174.4 (3)	C12—C11—C16—C15	−3.6 (6)
C2—C3—C4—N3	4.0 (6)	N2—C11—C16—C15	176.5 (3)
N1—C3—C4—S1	4.7 (5)	C14—C15—C16—C11	2.5 (6)
C2—C3—C4—S1	−176.9 (3)	C2—C1—C17—C18	123.4 (4)
C6—S1—C4—N3	0.4 (3)	N2—C1—C17—C18	−54.1 (5)
C6—S1—C4—C3	−178.8 (3)	C2—C1—C17—C22	−55.6 (5)
C4—N3—C5—C6	−0.4 (5)	N2—C1—C17—C22	126.9 (4)
C4—N3—C5—C10	178.2 (3)	C22—C17—C18—C19	−0.2 (5)
N3—C5—C6—C7	179.9 (3)	C1—C17—C18—C19	−179.2 (3)
C10—C5—C6—C7	1.4 (7)	C17—C18—C19—C20	0.2 (6)
N3—C5—C6—S1	0.7 (4)	C18—C19—C20—C21	−0.1 (6)
C10—C5—C6—S1	−177.8 (3)	C18—C19—C20—Cl1	178.8 (3)
C4—S1—C6—C5	−0.6 (3)	C19—C20—C21—C22	0.0 (6)
C4—S1—C6—C7	−179.8 (3)	Cl1—C20—C21—C22	−178.9 (3)
C8—O1—C7—O2	−2.1 (6)	C20—C21—C22—C17	0.0 (6)
C8—O1—C7—C6	178.0 (3)	C18—C17—C22—C21	0.1 (5)
C5—C6—C7—O2	3.9 (6)	C1—C17—C22—C21	179.1 (3)
S1—C6—C7—O2	−177.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15A···O2i	0.93	2.48	3.251 (5)	141

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15A⋯O2i	0.93	2.48	3.251 (5)	141

Symmetry code: (i) .