2-[3-(4-Bromo-phenyl)-5-(4-fluoro-phenyl)-4,5-di-hydro-1H-pyrazol-1-yl]-4-phenyl-1,3-thia-zole.

In the title compound, C24H17BrFN3S, the pyrazole ring is almost planar (r.m.s. deviation = 0.043 Å), with all but the perpendicular fluoro-benzene ring substituents [dihedral angle = 77.9 (3)°] being very approximately coplanar [dihedral angle with the 2-thienyl ring = 19.4 (3)° and with the bromo-benzene ring = 20.3 (3)°; dihedral angle between the 2-thienyl and attached phenyl ring = 11.0 (4)°], so that the mol-ecule has a T-shape. In the crystal, supra-molecular chains along the b-axis direction are sustained by C-H⋯S and C-Br⋯π inter-actions.

Related literature

For the biological activities and synthesis of pyrazolin-1-carbo­thio­amides, see: Abdel-Wahab et al. (2012 ▶); Lv et al. (2011 ▶). For a related structure, see: Abdel-Wahab et al. (2013 ▶).

Experimental

Crystal data

C24H17BrFN3S

M = 478.38

Monoclinic,

a = 13.747 (2) Å

b = 5.6695 (13) Å

c = 14.280 (3) Å

β = 106.94 (2)°

V = 1064.7 (4) Å3

Z = 2

Mo Kα radiation

μ = 2.05 mm−1

T = 295 K

0.30 × 0.10 × 0.02 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.937, T max = 1.000

7430 measured reflections

4124 independent reflections

1947 reflections with I > 2σ(I)

R int = 0.052

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.136

S = 0.95

4124 reflections

271 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.32 e Å−3

Absolute structure: Flack (1983 ▶), 1440 Friedel pairs

Flack parameter: −0.022 (15)

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/S1600536813010039/qm2094sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813010039/qm2094Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813010039/qm2094Isup3.cml

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

C24H17BrFN3S	F(000) = 484
Mr = 478.38	Dx = 1.492 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1208 reflections
a = 13.747 (2) Å	θ = 2.9–27.5°
b = 5.6695 (13) Å	µ = 2.05 mm−1
c = 14.280 (3) Å	T = 295 K
β = 106.94 (2)°	Plate, yellow
V = 1064.7 (4) Å3	0.30 × 0.10 × 0.02 mm
Z = 2

Agilent SuperNova Dual diffractometer with an Atlas detector	4124 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1947 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.052
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 2.9°
ω scan	h = −17→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −7→7
Tmin = 0.937, Tmax = 1.000	l = −17→18
7430 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052	H-atom parameters constrained
wR(F2) = 0.136	w = 1/[σ2(Fo2) + (0.042P)2] where P = (Fo2 + 2Fc2)/3
S = 0.95	(Δ/σ)max < 0.001
4124 reflections	Δρmax = 0.26 e Å−3
271 parameters	Δρmin = −0.32 e Å−3
1 restraint	Absolute structure: Flack (1983), 1440 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.022 (15)

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
Br1	0.80996 (5)	0.5031 (2)	1.12976 (5)	0.1040 (4)
S1	0.42126 (13)	0.7866 (3)	0.50255 (13)	0.0748 (5)
N1	0.2837 (3)	0.4642 (11)	0.4419 (4)	0.0630 (14)
N3	0.4367 (3)	0.5425 (12)	0.6880 (4)	0.0660 (14)
F1	−0.0906 (3)	0.3496 (8)	0.6421 (3)	0.1023 (14)
N2	0.3571 (4)	0.4670 (11)	0.6112 (4)	0.0710 (15)
C1	0.3593 (4)	0.7686 (14)	0.3793 (4)	0.0702 (18)
H1	0.3715	0.8689	0.3324	0.084*
C2	0.2906 (4)	0.5902 (12)	0.3589 (5)	0.0646 (18)
C3	0.3476 (4)	0.5541 (12)	0.5189 (5)	0.0594 (16)
C4	0.3109 (4)	0.2426 (12)	0.6306 (4)	0.0629 (17)
H4	0.3147	0.1233	0.5822	0.075*
C5	0.3835 (5)	0.1799 (13)	0.7310 (5)	0.075 (2)
H5A	0.3465	0.1557	0.7786	0.090*
H5B	0.4218	0.0383	0.7273	0.090*
C6	0.4522 (4)	0.3888 (12)	0.7575 (5)	0.0614 (17)
C7	0.2229 (4)	0.5194 (15)	0.2635 (4)	0.0657 (16)
C8	0.1643 (5)	0.3151 (14)	0.2503 (5)	0.077 (2)
H8	0.1693	0.2152	0.3032	0.092*
C9	0.0991 (5)	0.2595 (18)	0.1599 (6)	0.090 (2)
H9	0.0608	0.1220	0.1527	0.108*
C10	0.0896 (6)	0.4009 (16)	0.0809 (6)	0.089 (3)
H10	0.0448	0.3605	0.0205	0.107*
C11	0.1458 (6)	0.6017 (16)	0.0904 (6)	0.086 (2)
H11	0.1399	0.6990	0.0366	0.103*
C12	0.2119 (5)	0.6601 (13)	0.1811 (5)	0.073 (2)
H12	0.2501	0.7976	0.1870	0.088*
C13	0.2020 (4)	0.2804 (12)	0.6295 (4)	0.0513 (14)
C14	0.1304 (4)	0.1072 (11)	0.5906 (4)	0.0625 (17)
H14	0.1488	−0.0251	0.5612	0.075*
C15	0.0310 (5)	0.1304 (13)	0.5955 (5)	0.0724 (19)
H15	−0.0176	0.0157	0.5691	0.087*
C16	0.0072 (5)	0.3227 (15)	0.6393 (5)	0.0688 (19)
C17	0.0750 (5)	0.4978 (15)	0.6783 (4)	0.0709 (16)
H17	0.0552	0.6299	0.7067	0.085*
C18	0.1738 (5)	0.4744 (15)	0.6745 (4)	0.0679 (17)
H18	0.2217	0.5895	0.7023	0.081*
C19	0.5332 (5)	0.4234 (12)	0.8500 (5)	0.0619 (18)
C20	0.5968 (5)	0.6173 (13)	0.8638 (5)	0.074 (2)
H20	0.5849	0.7331	0.8156	0.089*
C21	0.6774 (5)	0.6428 (13)	0.9471 (5)	0.077 (2)
H21	0.7196	0.7741	0.9548	0.092*
C22	0.6949 (5)	0.4748 (17)	1.0181 (4)	0.0730 (19)
C23	0.6317 (5)	0.2821 (15)	1.0095 (5)	0.076 (2)
H23	0.6431	0.1703	1.0592	0.091*
C24	0.5504 (5)	0.2581 (15)	0.9248 (5)	0.0751 (19)
H24	0.5069	0.1295	0.9183	0.090*

	U11	U22	U33	U12	U13	U23
Br1	0.0919 (5)	0.1352 (8)	0.0810 (5)	0.0014 (6)	0.0188 (4)	−0.0233 (6)
S1	0.0741 (10)	0.0648 (12)	0.0979 (12)	−0.0075 (10)	0.0447 (10)	−0.0009 (10)
N1	0.052 (3)	0.063 (4)	0.081 (3)	0.003 (3)	0.031 (3)	0.019 (3)
N3	0.055 (3)	0.068 (4)	0.080 (3)	−0.002 (3)	0.028 (3)	0.002 (4)
F1	0.070 (2)	0.097 (3)	0.157 (4)	−0.005 (2)	0.060 (3)	−0.005 (3)
N2	0.065 (3)	0.068 (4)	0.081 (3)	−0.010 (3)	0.024 (3)	0.017 (3)
C1	0.076 (4)	0.067 (5)	0.079 (4)	0.009 (4)	0.040 (4)	0.006 (4)
C2	0.055 (3)	0.059 (5)	0.090 (5)	0.001 (3)	0.036 (4)	−0.001 (4)
C3	0.048 (3)	0.058 (5)	0.081 (4)	0.005 (3)	0.032 (3)	0.005 (4)
C4	0.068 (4)	0.048 (4)	0.077 (4)	−0.006 (3)	0.028 (4)	0.005 (3)
C5	0.063 (4)	0.063 (5)	0.100 (5)	0.000 (4)	0.027 (4)	0.013 (4)
C6	0.052 (4)	0.055 (4)	0.080 (4)	0.002 (3)	0.024 (3)	0.006 (4)
C7	0.060 (3)	0.063 (5)	0.083 (4)	0.005 (4)	0.035 (3)	0.014 (5)
C8	0.082 (4)	0.063 (5)	0.092 (5)	0.008 (4)	0.036 (4)	0.010 (4)
C9	0.072 (4)	0.100 (7)	0.094 (6)	−0.013 (5)	0.020 (4)	0.007 (5)
C10	0.073 (5)	0.107 (8)	0.087 (5)	0.013 (5)	0.024 (4)	0.023 (5)
C11	0.080 (5)	0.091 (7)	0.094 (6)	0.005 (5)	0.036 (5)	0.028 (5)
C12	0.070 (4)	0.067 (5)	0.088 (5)	0.001 (4)	0.031 (4)	0.016 (4)
C13	0.050 (3)	0.052 (4)	0.052 (3)	−0.007 (3)	0.014 (3)	0.007 (3)
C14	0.065 (4)	0.048 (4)	0.071 (4)	−0.001 (3)	0.015 (3)	0.001 (3)
C15	0.066 (4)	0.062 (5)	0.091 (5)	−0.022 (4)	0.026 (4)	−0.008 (4)
C16	0.066 (4)	0.074 (6)	0.074 (4)	0.007 (4)	0.032 (4)	0.010 (4)
C17	0.081 (4)	0.051 (4)	0.085 (4)	0.002 (5)	0.031 (4)	−0.007 (4)
C18	0.067 (4)	0.059 (5)	0.083 (4)	−0.004 (4)	0.029 (3)	−0.006 (4)
C19	0.056 (4)	0.056 (5)	0.081 (4)	−0.001 (3)	0.031 (3)	−0.009 (4)
C20	0.080 (5)	0.062 (5)	0.084 (5)	0.008 (4)	0.028 (4)	0.006 (4)
C21	0.067 (4)	0.064 (5)	0.098 (5)	−0.006 (4)	0.022 (4)	−0.018 (5)
C22	0.066 (4)	0.086 (6)	0.074 (4)	0.015 (5)	0.031 (3)	−0.003 (5)
C23	0.080 (4)	0.079 (5)	0.074 (5)	0.002 (5)	0.030 (4)	0.011 (4)
C24	0.076 (4)	0.069 (5)	0.085 (5)	0.001 (4)	0.030 (4)	−0.001 (4)

Br1—C22	1.897 (6)	C10—C11	1.360 (10)
S1—C3	1.719 (7)	C10—H10	0.9300
S1—C1	1.720 (6)	C11—C12	1.388 (9)
N1—C3	1.295 (7)	C11—H11	0.9300
N1—C2	1.411 (7)	C12—H12	0.9300
N3—C6	1.290 (8)	C13—C18	1.384 (9)
N3—N2	1.373 (6)	C13—C14	1.386 (8)
F1—C16	1.365 (7)	C14—C15	1.395 (8)
N2—C3	1.378 (7)	C14—H14	0.9300
N2—C4	1.483 (8)	C15—C16	1.344 (9)
C1—C2	1.357 (8)	C15—H15	0.9300
C1—H1	0.9300	C16—C17	1.364 (10)
C2—C7	1.464 (8)	C17—C18	1.382 (8)
C4—C13	1.508 (7)	C17—H17	0.9300
C4—C5	1.531 (8)	C18—H18	0.9300
C4—H4	0.9800	C19—C24	1.388 (10)
C5—C6	1.493 (8)	C19—C20	1.383 (9)
C5—H5A	0.9700	C20—C21	1.377 (9)
C5—H5B	0.9700	C20—H20	0.9300
C6—C19	1.472 (9)	C21—C22	1.361 (10)
C7—C12	1.392 (8)	C21—H21	0.9300
C7—C8	1.392 (10)	C22—C23	1.379 (11)
C8—C9	1.377 (9)	C23—C24	1.394 (8)
C8—H8	0.9300	C23—H23	0.9300
C9—C10	1.358 (10)	C24—H24	0.9300
C9—H9	0.9300
C3—S1—C1	87.6 (3)	C10—C11—C12	119.5 (8)
C3—N1—C2	108.7 (5)	C10—C11—H11	120.3
C6—N3—N2	108.5 (6)	C12—C11—H11	120.3
N3—N2—C3	118.9 (5)	C11—C12—C7	122.1 (7)
N3—N2—C4	113.8 (5)	C11—C12—H12	118.9
C3—N2—C4	124.1 (6)	C7—C12—H12	118.9
C2—C1—S1	111.7 (5)	C18—C13—C14	119.2 (5)
C2—C1—H1	124.1	C18—C13—C4	121.2 (6)
S1—C1—H1	124.1	C14—C13—C4	119.4 (6)
C1—C2—N1	114.2 (6)	C13—C14—C15	120.3 (6)
C1—C2—C7	128.2 (6)	C13—C14—H14	119.9
N1—C2—C7	117.6 (6)	C15—C14—H14	119.9
N1—C3—N2	121.5 (6)	C16—C15—C14	118.4 (6)
N1—C3—S1	117.8 (5)	C16—C15—H15	120.8
N2—C3—S1	120.6 (5)	C14—C15—H15	120.8
N2—C4—C13	110.7 (5)	C15—C16—F1	118.7 (7)
N2—C4—C5	100.2 (5)	C15—C16—C17	123.3 (6)
C13—C4—C5	114.7 (5)	F1—C16—C17	118.0 (7)
N2—C4—H4	110.3	C16—C17—C18	118.5 (7)
C13—C4—H4	110.3	C16—C17—H17	120.8
C5—C4—H4	110.3	C18—C17—H17	120.8
C6—C5—C4	104.1 (5)	C13—C18—C17	120.4 (7)
C6—C5—H5A	110.9	C13—C18—H18	119.8
C4—C5—H5A	110.9	C17—C18—H18	119.8
C6—C5—H5B	110.9	C24—C19—C20	117.9 (6)
C4—C5—H5B	110.9	C24—C19—C6	121.0 (6)
H5A—C5—H5B	108.9	C20—C19—C6	121.0 (6)
N3—C6—C19	120.8 (6)	C21—C20—C19	121.5 (7)
N3—C6—C5	113.0 (5)	C21—C20—H20	119.2
C19—C6—C5	126.1 (6)	C19—C20—H20	119.2
C12—C7—C8	116.5 (6)	C22—C21—C20	119.6 (7)
C12—C7—C2	120.8 (7)	C22—C21—H21	120.2
C8—C7—C2	122.6 (6)	C20—C21—H21	120.2
C9—C8—C7	120.7 (7)	C21—C22—C23	121.2 (6)
C9—C8—H8	119.7	C21—C22—Br1	119.4 (6)
C7—C8—H8	119.7	C23—C22—Br1	119.5 (6)
C10—C9—C8	121.5 (8)	C22—C23—C24	118.7 (7)
C10—C9—H9	119.2	C22—C23—H23	120.6
C8—C9—H9	119.2	C24—C23—H23	120.6
C9—C10—C11	119.7 (8)	C19—C24—C23	121.0 (7)
C9—C10—H10	120.1	C19—C24—H24	119.5
C11—C10—H10	120.1	C23—C24—H24	119.5
C6—N3—N2—C3	−158.5 (6)	C9—C10—C11—C12	−0.3 (11)
C6—N3—N2—C4	2.0 (7)	C10—C11—C12—C7	−0.1 (11)
C3—S1—C1—C2	−1.3 (5)	C8—C7—C12—C11	0.4 (10)
S1—C1—C2—N1	1.2 (7)	C2—C7—C12—C11	−177.8 (6)
S1—C1—C2—C7	179.6 (5)	N2—C4—C13—C18	−42.9 (8)
C3—N1—C2—C1	−0.3 (7)	C5—C4—C13—C18	69.5 (8)
C3—N1—C2—C7	−178.9 (5)	N2—C4—C13—C14	143.0 (6)
C2—N1—C3—N2	179.6 (5)	C5—C4—C13—C14	−104.5 (6)
C2—N1—C3—S1	−0.7 (7)	C18—C13—C14—C15	1.0 (9)
N3—N2—C3—N1	169.5 (6)	C4—C13—C14—C15	175.2 (6)
C4—N2—C3—N1	11.1 (9)	C13—C14—C15—C16	−0.6 (9)
N3—N2—C3—S1	−10.2 (8)	C14—C15—C16—F1	178.3 (6)
C4—N2—C3—S1	−168.5 (4)	C14—C15—C16—C17	0.8 (11)
C1—S1—C3—N1	1.2 (5)	C15—C16—C17—C18	−1.5 (10)
C1—S1—C3—N2	−179.1 (6)	F1—C16—C17—C18	−179.0 (6)
N3—N2—C4—C13	116.3 (5)	C14—C13—C18—C17	−1.6 (9)
C3—N2—C4—C13	−84.3 (7)	C4—C13—C18—C17	−175.7 (6)
N3—N2—C4—C5	−5.1 (6)	C16—C17—C18—C13	1.9 (9)
C3—N2—C4—C5	154.3 (6)	N3—C6—C19—C24	−179.8 (6)
N2—C4—C5—C6	5.8 (6)	C5—C6—C19—C24	−2.2 (10)
C13—C4—C5—C6	−112.8 (6)	N3—C6—C19—C20	−2.1 (9)
N2—N3—C6—C19	−179.7 (5)	C5—C6—C19—C20	175.5 (6)
N2—N3—C6—C5	2.4 (7)	C24—C19—C20—C21	2.5 (10)
C4—C5—C6—N3	−5.5 (7)	C6—C19—C20—C21	−175.2 (6)
C4—C5—C6—C19	176.7 (6)	C19—C20—C21—C22	−0.4 (10)
C1—C2—C7—C12	−10.0 (10)	C20—C21—C22—C23	−1.8 (11)
N1—C2—C7—C12	168.3 (6)	C20—C21—C22—Br1	176.9 (5)
C1—C2—C7—C8	172.0 (6)	C21—C22—C23—C24	1.8 (10)
N1—C2—C7—C8	−9.7 (9)	Br1—C22—C23—C24	−176.9 (5)
C12—C7—C8—C9	−0.3 (10)	C20—C19—C24—C23	−2.5 (10)
C2—C7—C8—C9	177.8 (6)	C6—C19—C24—C23	175.2 (6)
C7—C8—C9—C10	−0.1 (11)	C22—C23—C24—C19	0.4 (10)
C8—C9—C10—C11	0.4 (12)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···S1i	0.98	2.84	3.734 (7)	153
C22—Br1···Cg1ii	1.90 (1)	3.64 (1)	5.265 (7)	142 (1)

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C13–C18 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯S1i	0.98	2.84	3.734 (7)	153
C22—Br1⋯Cg1ii	1.897 (6)	3.644 (3)	5.265 (7)	141.6 (3)

Symmetry codes: (i) ; (ii) .