2-[3-(4-Chloro-phen-yl)-5-(4-fluoro-phenyl)-4,5-dihydro-1H-pyrazol-1-yl]-4-phenyl-1,3-thia-zole.

In the title compound, C24H17ClFN3S, the pyrazole ring is almost planar (r.m.s. deviation = 0.030 Å). With the exception of the methine-bound benzene ring, which forms a dihedral angle of 85.77 (13)° with the pyrazole ring, the remaining non-C atoms lie in an approximate plane (r.m.s. deviation = 0.084 Å) so that overall the mol-ecule has a T-shape. In the crystal, centrosymmetrically related mol-ecules are connected via π-π inter-actions between pyrazole rings [centroid-centroid distance = 3.5370 (15) Å] and these stack along the a axis with no specific inter-actions between them.

Related literature

For the biological activity of pyrazolin-1-carbothio­amides, see: Abdel-Wahab et al. (2009 ▶, 2012 ▶); Lv et al. (2011 ▶); Chimenti et al. (2010 ▶). For a related structure, see: Abdel-Wahab et al. (2013 ▶).

Experimental

Crystal data

C24H17ClFN3S

M = 433.92

Monoclinic,

a = 11.1360 (9) Å

b = 16.4129 (16) Å

c = 11.6066 (7) Å

β = 98.170 (7)°

V = 2099.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.31 mm−1

T = 295 K

0.25 × 0.25 × 0.25 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.956, T max = 1.000

11642 measured reflections

4850 independent reflections

2627 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.140

S = 1.03

4850 reflections

271 parameters

H-atom parameters constrained

Δρmax = 0.17 e Å−3

Δρmin = −0.28 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); 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: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813007496/hb7058sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007496/hb7058Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813007496/hb7058Isup3.cml

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

C24H17ClFN3S	F(000) = 896
Mr = 433.92	Dx = 1.373 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2134 reflections
a = 11.1360 (9) Å	θ = 3.0–27.5°
b = 16.4129 (16) Å	µ = 0.31 mm−1
c = 11.6066 (7) Å	T = 295 K
β = 98.170 (7)°	Cube, yellow
V = 2099.9 (3) Å3	0.25 × 0.25 × 0.25 mm
Z = 4

Agilent SuperNova Dual diffractometer with an Atlas detector	4850 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2627 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.043
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 3.0°
ω scan	h = −14→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −21→21
Tmin = 0.956, Tmax = 1.000	l = −15→14
11642 measured reflections

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0448P)2 + 0.1993P] where P = (Fo2 + 2Fc2)/3
4850 reflections	(Δ/σ)max = 0.001
271 parameters	Δρmax = 0.17 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

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
Cl1	0.78673 (9)	0.63985 (7)	1.06121 (7)	0.1183 (4)
S1	0.51447 (6)	0.68324 (4)	0.29541 (5)	0.0663 (2)
N1	0.30894 (17)	0.61006 (12)	0.23548 (15)	0.0540 (5)
N2	0.38567 (17)	0.59931 (14)	0.43352 (16)	0.0635 (6)
N3	0.48128 (17)	0.61670 (12)	0.51903 (16)	0.0576 (5)
C1	0.2574 (2)	0.64048 (14)	0.02591 (19)	0.0550 (6)
C2	0.1497 (3)	0.59731 (18)	0.0197 (2)	0.0774 (8)
H2	0.1309	0.5703	0.0852	0.093*
C3	0.0700 (3)	0.5940 (2)	−0.0830 (2)	0.0925 (10)
H3	−0.0015	0.5643	−0.0863	0.111*
C4	0.0959 (3)	0.63419 (19)	−0.1797 (2)	0.0851 (9)
H4	0.0421	0.6318	−0.2487	0.102*
C5	0.2002 (3)	0.67765 (18)	−0.1749 (2)	0.0817 (9)
H5	0.2173	0.7057	−0.2403	0.098*
C6	0.2807 (3)	0.68030 (16)	−0.0734 (2)	0.0708 (8)
H6	0.3525	0.7096	−0.0716	0.085*
C8	0.4471 (2)	0.68840 (16)	0.1533 (2)	0.0649 (7)
H8	0.4796	0.7162	0.0951	0.078*
C9	0.3406 (2)	0.64703 (14)	0.13609 (19)	0.0544 (6)
C10	0.3922 (2)	0.62494 (14)	0.32298 (19)	0.0528 (6)
C11	0.2942 (2)	0.54327 (15)	0.47086 (19)	0.0555 (6)
H11	0.2985	0.4907	0.4317	0.067*
C12	0.3456 (2)	0.53387 (16)	0.60180 (19)	0.0600 (7)
H12A	0.2901	0.5562	0.6509	0.072*
H12B	0.3609	0.4771	0.6220	0.072*
C13	0.4618 (2)	0.58159 (15)	0.6141 (2)	0.0537 (6)
C14	0.5449 (2)	0.59300 (15)	0.72236 (19)	0.0544 (6)
C15	0.5162 (2)	0.56281 (17)	0.8256 (2)	0.0708 (7)
H15	0.4455	0.5328	0.8258	0.085*
C16	0.5917 (3)	0.5766 (2)	0.9296 (2)	0.0829 (9)
H16	0.5713	0.5563	0.9991	0.099*
C17	0.6964 (3)	0.62029 (19)	0.9294 (2)	0.0748 (8)
C18	0.7284 (2)	0.64998 (17)	0.8275 (2)	0.0719 (8)
H18	0.8003	0.6788	0.8279	0.086*
C19	0.6529 (2)	0.63669 (16)	0.7247 (2)	0.0624 (7)
H19	0.6742	0.6571	0.6556	0.075*
C20	0.1672 (2)	0.57571 (15)	0.44605 (17)	0.0513 (6)
C21	0.0808 (2)	0.53493 (17)	0.3704 (2)	0.0658 (7)
H21	0.1030	0.4882	0.3333	0.079*
C22	−0.0367 (3)	0.5615 (2)	0.3486 (2)	0.0814 (9)
H22	−0.0942	0.5334	0.2975	0.098*
C23	−0.0668 (2)	0.6295 (2)	0.4033 (3)	0.0812 (9)
C24	0.0139 (3)	0.67373 (18)	0.4776 (2)	0.0763 (8)
H24	−0.0096	0.7208	0.5130	0.092*
C25	0.1323 (2)	0.64571 (16)	0.4982 (2)	0.0626 (7)
H25	0.1895	0.6747	0.5482	0.075*
F1	−0.18491 (17)	0.65571 (14)	0.3846 (2)	0.1352 (8)

	U11	U22	U33	U12	U13	U23
Cl1	0.1101 (7)	0.1603 (10)	0.0746 (5)	−0.0153 (6)	−0.0217 (5)	−0.0053 (5)
S1	0.0548 (4)	0.0757 (5)	0.0696 (4)	−0.0128 (3)	0.0131 (3)	0.0027 (3)
N1	0.0499 (12)	0.0621 (13)	0.0519 (11)	−0.0029 (9)	0.0140 (9)	0.0029 (9)
N2	0.0474 (12)	0.0907 (16)	0.0525 (11)	−0.0160 (11)	0.0075 (9)	0.0026 (10)
N3	0.0467 (12)	0.0678 (14)	0.0590 (11)	−0.0024 (10)	0.0097 (9)	−0.0021 (10)
C1	0.0615 (16)	0.0520 (15)	0.0537 (13)	−0.0006 (12)	0.0155 (11)	0.0003 (11)
C2	0.082 (2)	0.086 (2)	0.0635 (16)	−0.0220 (17)	0.0072 (14)	0.0121 (14)
C3	0.090 (2)	0.108 (3)	0.0753 (19)	−0.0319 (19)	−0.0035 (17)	0.0120 (17)
C4	0.103 (3)	0.089 (2)	0.0588 (16)	−0.0135 (19)	−0.0031 (16)	−0.0019 (15)
C5	0.114 (3)	0.081 (2)	0.0521 (15)	−0.0105 (19)	0.0169 (16)	0.0027 (14)
C6	0.085 (2)	0.0721 (19)	0.0583 (15)	−0.0137 (15)	0.0200 (14)	0.0003 (13)
C8	0.0638 (17)	0.0667 (18)	0.0669 (15)	−0.0105 (13)	0.0190 (13)	0.0060 (13)
C9	0.0568 (15)	0.0511 (15)	0.0579 (13)	0.0013 (12)	0.0172 (12)	−0.0001 (11)
C10	0.0464 (14)	0.0572 (15)	0.0575 (13)	0.0015 (11)	0.0170 (11)	0.0014 (11)
C11	0.0488 (14)	0.0612 (16)	0.0580 (13)	−0.0038 (11)	0.0133 (11)	−0.0046 (11)
C12	0.0509 (15)	0.0692 (18)	0.0602 (14)	0.0021 (12)	0.0083 (11)	0.0079 (12)
C13	0.0457 (14)	0.0577 (15)	0.0582 (13)	0.0046 (11)	0.0090 (11)	0.0011 (12)
C14	0.0530 (15)	0.0545 (15)	0.0559 (13)	0.0088 (12)	0.0080 (11)	−0.0006 (11)
C15	0.0639 (17)	0.084 (2)	0.0639 (15)	−0.0053 (14)	0.0065 (13)	0.0087 (14)
C16	0.086 (2)	0.102 (3)	0.0598 (16)	−0.0041 (18)	0.0054 (15)	0.0133 (15)
C17	0.0692 (19)	0.083 (2)	0.0674 (17)	0.0049 (16)	−0.0061 (14)	−0.0028 (15)
C18	0.0583 (17)	0.076 (2)	0.0782 (18)	−0.0008 (14)	0.0007 (14)	−0.0073 (15)
C19	0.0575 (16)	0.0656 (17)	0.0639 (14)	0.0014 (13)	0.0078 (12)	−0.0024 (12)
C20	0.0474 (14)	0.0630 (16)	0.0448 (11)	−0.0062 (11)	0.0110 (10)	0.0028 (11)
C21	0.0568 (16)	0.0739 (19)	0.0666 (15)	−0.0072 (13)	0.0078 (12)	−0.0090 (13)
C22	0.0596 (19)	0.097 (3)	0.0828 (19)	−0.0129 (16)	−0.0055 (15)	0.0028 (17)
C23	0.0462 (17)	0.096 (2)	0.100 (2)	0.0062 (16)	0.0039 (16)	0.0247 (19)
C24	0.073 (2)	0.0684 (19)	0.0896 (19)	0.0136 (15)	0.0176 (16)	0.0093 (15)
C25	0.0616 (17)	0.0636 (18)	0.0627 (14)	−0.0039 (13)	0.0087 (13)	0.0018 (13)
F1	0.0629 (12)	0.1386 (19)	0.197 (2)	0.0270 (11)	−0.0043 (13)	0.0207 (15)

Cl1—C17	1.737 (2)	C12—C13	1.501 (3)
S1—C8	1.714 (2)	C12—H12A	0.9700
S1—C10	1.731 (2)	C12—H12B	0.9700
N1—C10	1.297 (3)	C13—C14	1.463 (3)
N1—C9	1.392 (3)	C14—C15	1.376 (3)
N2—C10	1.362 (3)	C14—C19	1.398 (3)
N2—N3	1.378 (2)	C15—C16	1.388 (3)
N2—C11	1.482 (3)	C15—H15	0.9300
N3—C13	1.290 (3)	C16—C17	1.369 (4)
C1—C6	1.381 (3)	C16—H16	0.9300
C1—C2	1.386 (3)	C17—C18	1.373 (4)
C1—C9	1.472 (3)	C18—C19	1.375 (3)
C2—C3	1.382 (3)	C18—H18	0.9300
C2—H2	0.9300	C19—H19	0.9300
C3—C4	1.368 (4)	C20—C21	1.380 (3)
C3—H3	0.9300	C20—C25	1.380 (3)
C4—C5	1.358 (4)	C21—C22	1.368 (4)
C4—H4	0.9300	C21—H21	0.9300
C5—C6	1.376 (3)	C22—C23	1.350 (4)
C5—H5	0.9300	C22—H22	0.9300
C6—H6	0.9300	C23—C24	1.363 (4)
C8—C9	1.357 (3)	C23—F1	1.371 (3)
C8—H8	0.9300	C24—C25	1.384 (4)
C11—C20	1.500 (3)	C24—H24	0.9300
C11—C12	1.554 (3)	C25—H25	0.9300
C11—H11	0.9800
C8—S1—C10	87.52 (12)	C13—C12—H12B	111.1
C10—N1—C9	109.26 (19)	C11—C12—H12B	111.1
C10—N2—N3	118.38 (19)	H12A—C12—H12B	109.0
C10—N2—C11	126.72 (18)	N3—C13—C14	121.0 (2)
N3—N2—C11	114.24 (17)	N3—C13—C12	113.54 (19)
C13—N3—N2	108.45 (19)	C14—C13—C12	125.4 (2)
C6—C1—C2	117.5 (2)	C15—C14—C19	118.2 (2)
C6—C1—C9	121.4 (2)	C15—C14—C13	120.4 (2)
C2—C1—C9	121.0 (2)	C19—C14—C13	121.3 (2)
C3—C2—C1	120.7 (3)	C14—C15—C16	120.8 (3)
C3—C2—H2	119.7	C14—C15—H15	119.6
C1—C2—H2	119.7	C16—C15—H15	119.6
C4—C3—C2	120.3 (3)	C17—C16—C15	119.6 (3)
C4—C3—H3	119.9	C17—C16—H16	120.2
C2—C3—H3	119.9	C15—C16—H16	120.2
C5—C4—C3	119.9 (3)	C16—C17—C18	120.8 (2)
C5—C4—H4	120.0	C16—C17—Cl1	118.8 (2)
C3—C4—H4	120.0	C18—C17—Cl1	120.3 (2)
C4—C5—C6	120.1 (3)	C17—C18—C19	119.3 (3)
C4—C5—H5	120.0	C17—C18—H18	120.3
C6—C5—H5	120.0	C19—C18—H18	120.3
C5—C6—C1	121.5 (3)	C18—C19—C14	121.1 (3)
C5—C6—H6	119.2	C18—C19—H19	119.5
C1—C6—H6	119.2	C14—C19—H19	119.5
C9—C8—S1	111.78 (19)	C21—C20—C25	117.9 (2)
C9—C8—H8	124.1	C21—C20—C11	120.2 (2)
S1—C8—H8	124.1	C25—C20—C11	121.9 (2)
C8—C9—N1	114.5 (2)	C22—C21—C20	121.7 (3)
C8—C9—C1	126.4 (2)	C22—C21—H21	119.2
N1—C9—C1	119.1 (2)	C20—C21—H21	119.2
N1—C10—N2	123.5 (2)	C23—C22—C21	118.1 (3)
N1—C10—S1	116.92 (17)	C23—C22—H22	121.0
N2—C10—S1	119.57 (17)	C21—C22—H22	121.0
N2—C11—C20	113.08 (19)	C22—C23—C24	123.5 (3)
N2—C11—C12	100.03 (17)	C22—C23—F1	118.8 (3)
C20—C11—C12	115.44 (19)	C24—C23—F1	117.6 (3)
N2—C11—H11	109.3	C23—C24—C25	117.3 (3)
C20—C11—H11	109.3	C23—C24—H24	121.4
C12—C11—H11	109.3	C25—C24—H24	121.4
C13—C12—C11	103.54 (19)	C20—C25—C24	121.4 (2)
C13—C12—H12A	111.1	C20—C25—H25	119.3
C11—C12—H12A	111.1	C24—C25—H25	119.3
C10—N2—N3—C13	−174.7 (2)	N2—N3—C13—C14	−176.4 (2)
C11—N2—N3—C13	−3.4 (3)	N2—N3—C13—C12	0.5 (3)
C6—C1—C2—C3	0.7 (4)	C11—C12—C13—N3	2.3 (3)
C9—C1—C2—C3	177.6 (3)	C11—C12—C13—C14	179.0 (2)
C1—C2—C3—C4	−0.8 (5)	N3—C13—C14—C15	172.7 (2)
C2—C3—C4—C5	−0.1 (5)	C12—C13—C14—C15	−3.8 (4)
C3—C4—C5—C6	0.9 (5)	N3—C13—C14—C19	−5.3 (4)
C4—C5—C6—C1	−1.0 (4)	C12—C13—C14—C19	178.2 (2)
C2—C1—C6—C5	0.2 (4)	C19—C14—C15—C16	1.1 (4)
C9—C1—C6—C5	−176.7 (2)	C13—C14—C15—C16	−176.9 (2)
C10—S1—C8—C9	−0.2 (2)	C14—C15—C16—C17	−0.5 (5)
S1—C8—C9—N1	0.2 (3)	C15—C16—C17—C18	−0.6 (5)
S1—C8—C9—C1	178.26 (19)	C15—C16—C17—Cl1	177.8 (2)
C10—N1—C9—C8	0.0 (3)	C16—C17—C18—C19	1.1 (4)
C10—N1—C9—C1	−178.2 (2)	Cl1—C17—C18—C19	−177.3 (2)
C6—C1—C9—C8	−2.2 (4)	C17—C18—C19—C14	−0.5 (4)
C2—C1—C9—C8	−178.9 (3)	C15—C14—C19—C18	−0.6 (4)
C6—C1—C9—N1	175.8 (2)	C13—C14—C19—C18	177.4 (2)
C2—C1—C9—N1	−0.9 (4)	N2—C11—C20—C21	117.2 (2)
C9—N1—C10—N2	177.8 (2)	C12—C11—C20—C21	−128.4 (2)
C9—N1—C10—S1	−0.2 (3)	N2—C11—C20—C25	−63.6 (3)
N3—N2—C10—N1	178.1 (2)	C12—C11—C20—C25	50.8 (3)
C11—N2—C10—N1	8.0 (4)	C25—C20—C21—C22	−1.2 (4)
N3—N2—C10—S1	−3.9 (3)	C11—C20—C21—C22	178.0 (2)
C11—N2—C10—S1	−174.08 (19)	C20—C21—C22—C23	0.1 (4)
C8—S1—C10—N1	0.3 (2)	C21—C22—C23—C24	1.0 (5)
C8—S1—C10—N2	−177.8 (2)	C21—C22—C23—F1	−178.4 (3)
C10—N2—C11—C20	−61.7 (3)	C22—C23—C24—C25	−1.0 (5)
N3—N2—C11—C20	127.8 (2)	F1—C23—C24—C25	178.4 (2)
C10—N2—C11—C12	175.0 (2)	C21—C20—C25—C24	1.3 (4)
N3—N2—C11—C12	4.5 (3)	C11—C20—C25—C24	−177.9 (2)
N2—C11—C12—C13	−3.7 (2)	C23—C24—C25—C20	−0.2 (4)
C20—C11—C12—C13	−125.4 (2)