5-(4-Fluoro­phen­yl)-1-[4-(4-methyl­phen­yl)thia­zol-2-yl]-3-[4-(prop-2-yn­yloxy)phen­yl]-4,5-di­hydro-1H-pyrazole

In the title compound, C₂₈H₂₂FN₃OS, four rings are almost coplanar, with the fluorophenyl ring substantially twisted. In the extended structure, aromatic π–π stacking inter­actions between the pyrazole ring and the tolyl ring link the mol­ecules into centrosymmetric dimers.

Computing details

Data collection: APEX 2 (Bruker, 2005); cell refinement: APEX 2 (Bruker, 2005); data reduction: APEX 2 (Bruker, 2005); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

5-(4-Fluorophenyl)-1-[4-(4-methylphenyl)thiazol-2-yl]-3-[4-(prop-2-ynyloxy)phenyl]-4,5-dihydro-1H-pyrazole

Crystal data

C28H22FN3OS	F(000) = 976
Mr = 467.54	Dx = 1.329 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.7859 (13) Å	Cell parameters from 8134 reflections
b = 14.5638 (16) Å	θ = 2.3–19.4°
c = 14.9956 (14) Å	µ = 0.17 mm^−1
β = 97.144 (3)°	T = 100 K
V = 2337.3 (4) Å^3	Prism, pale yellow
Z = 4	0.24 × 0.17 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer	3999 reflections with I > 2σ(I)
ω & φ scans	Rint = 0.055
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	θmax = 27.5°, θmin = 2.4°
Tmin = 0.667, Tmax = 0.740	h = −13→13
34158 measured reflections	k = −18→18
5339 independent reflections	l = −19→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.124	w = 1/[σ^2(Fo^2) + (0.0555P)^2 + 0.4922P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
5339 reflections	Δρmax = 0.21 e Å^−3
312 parameters	Δρmin = −0.24 e Å^−3
0 restraints

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.41974 (4)	0.50137 (3)	0.68772 (3)	0.05135 (14)
F1	0.30040 (14)	0.00083 (9)	0.45510 (11)	0.0947 (5)
O1	1.05115 (12)	0.28517 (9)	1.05004 (8)	0.0620 (4)
N1	0.55591 (13)	0.35607 (10)	0.64338 (9)	0.0504 (3)
N2	0.62314 (12)	0.36498 (9)	0.72765 (9)	0.0458 (3)
N3	0.40086 (11)	0.41449 (9)	0.53590 (9)	0.0416 (3)
C1	0.71955 (14)	0.31161 (11)	0.73107 (11)	0.0429 (4)
C2	0.72870 (16)	0.25989 (13)	0.64542 (11)	0.0519 (4)
H2A	0.725916	0.192751	0.655328	0.062*
H2B	0.806651	0.275473	0.620224	0.062*
C3	0.61252 (15)	0.29284 (11)	0.58290 (11)	0.0453 (4)
H3	0.639256	0.327907	0.531225	0.054*
C4	0.46340 (14)	0.41667 (10)	0.61583 (11)	0.0421 (3)
C5	0.30581 (16)	0.53433 (12)	0.60280 (11)	0.0501 (4)
H5	0.248195	0.582902	0.607499	0.060*
C6	0.30918 (15)	0.48190 (10)	0.52848 (11)	0.0415 (3)
C7	0.22498 (15)	0.48815 (10)	0.44307 (11)	0.0428 (4)
C8	0.11627 (19)	0.53946 (15)	0.43594 (13)	0.0641 (5)
H8	0.096611	0.573810	0.486179	0.077*
C9	0.0357 (2)	0.54138 (16)	0.35642 (14)	0.0711 (6)
H9	−0.038797	0.576647	0.353696	0.085*
C10	0.06012 (18)	0.49389 (12)	0.28146 (12)	0.0542 (4)
C11	0.16914 (18)	0.44361 (13)	0.28824 (12)	0.0554 (4)
H11	0.189312	0.410573	0.237352	0.066*
C12	0.25025 (16)	0.44011 (12)	0.36778 (11)	0.0499 (4)
H12	0.324148	0.404195	0.370509	0.060*
C13	−0.0308 (2)	0.49575 (16)	0.19603 (14)	0.0742 (6)
H13A	−0.115982	0.487080	0.210809	0.111*
H13B	−0.010253	0.446321	0.156014	0.111*
H13C	−0.024930	0.555058	0.165965	0.111*
C14	0.52458 (14)	0.21655 (11)	0.54827 (10)	0.0417 (3)
C15	0.50313 (16)	0.19735 (12)	0.45752 (11)	0.0513 (4)
H15	0.540276	0.234834	0.416283	0.062*
C16	0.42798 (18)	0.12400 (13)	0.42561 (13)	0.0605 (5)
H16	0.414806	0.109938	0.363286	0.073*
C17	0.37364 (18)	0.07275 (13)	0.48627 (15)	0.0615 (5)
C18	0.3914 (2)	0.08969 (13)	0.57641 (15)	0.0645 (5)
H18	0.352303	0.052768	0.617046	0.077*
C19	0.46802 (17)	0.16219 (12)	0.60694 (12)	0.0537 (4)
H19	0.481996	0.174834	0.669533	0.064*
C20	0.80833 (14)	0.30375 (11)	0.81275 (10)	0.0425 (3)
C21	0.79227 (15)	0.35436 (12)	0.88945 (11)	0.0484 (4)
H21	0.722761	0.394575	0.888410	0.058*
C22	0.87487 (16)	0.34712 (13)	0.96621 (11)	0.0515 (4)
H22	0.862460	0.382276	1.017719	0.062*
C23	0.97723 (15)	0.28819 (12)	0.96889 (11)	0.0459 (4)
C24	0.99600 (16)	0.23779 (12)	0.89378 (11)	0.0503 (4)
H24	1.065768	0.197771	0.895145	0.060*
C25	0.91183 (15)	0.24615 (12)	0.81614 (11)	0.0493 (4)
H25	0.925194	0.211853	0.764298	0.059*
C26	1.15665 (16)	0.22557 (13)	1.05765 (11)	0.0520 (4)
H26A	1.221624	0.250122	1.022969	0.062*
H26B	1.131967	0.163786	1.034290	0.062*
C27	1.20376 (17)	0.22073 (13)	1.15271 (12)	0.0553 (4)
C28	1.2393 (2)	0.21588 (18)	1.22951 (16)	0.0804 (7)
H28	1.256 (3)	0.209 (2)	1.2914 (19)	0.121 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0563 (3)	0.0476 (2)	0.0466 (2)	0.00514 (19)	−0.00782 (18)	−0.00366 (18)
F1	0.0895 (9)	0.0677 (8)	0.1199 (12)	−0.0298 (7)	−0.0144 (8)	−0.0172 (7)
O1	0.0650 (8)	0.0700 (8)	0.0460 (7)	0.0306 (7)	−0.0132 (6)	−0.0083 (6)
N1	0.0508 (8)	0.0449 (8)	0.0497 (8)	0.0081 (6)	−0.0162 (6)	−0.0063 (6)
N2	0.0465 (7)	0.0418 (7)	0.0454 (7)	0.0022 (6)	−0.0085 (6)	−0.0006 (6)
N3	0.0399 (7)	0.0379 (7)	0.0445 (7)	−0.0016 (5)	−0.0049 (5)	0.0027 (5)
C1	0.0404 (8)	0.0409 (8)	0.0454 (9)	−0.0008 (6)	−0.0026 (6)	0.0003 (7)
C2	0.0448 (9)	0.0569 (10)	0.0511 (10)	0.0043 (8)	−0.0060 (7)	−0.0070 (8)
C3	0.0450 (8)	0.0438 (9)	0.0447 (9)	0.0004 (7)	−0.0039 (7)	−0.0011 (7)
C4	0.0401 (8)	0.0359 (8)	0.0477 (9)	−0.0024 (6)	−0.0045 (6)	0.0026 (6)
C5	0.0523 (9)	0.0466 (9)	0.0487 (10)	0.0080 (8)	−0.0042 (7)	0.0019 (7)
C6	0.0406 (8)	0.0371 (8)	0.0454 (8)	−0.0012 (6)	−0.0003 (6)	0.0063 (6)
C7	0.0427 (8)	0.0383 (8)	0.0458 (9)	−0.0022 (6)	−0.0012 (7)	0.0060 (6)
C8	0.0623 (11)	0.0692 (12)	0.0569 (11)	0.0230 (10)	−0.0086 (9)	−0.0102 (9)
C9	0.0638 (12)	0.0771 (14)	0.0658 (13)	0.0250 (11)	−0.0178 (10)	−0.0050 (11)
C10	0.0587 (10)	0.0510 (10)	0.0489 (10)	−0.0079 (8)	−0.0096 (8)	0.0093 (8)
C11	0.0636 (11)	0.0578 (11)	0.0435 (9)	−0.0051 (9)	0.0017 (8)	0.0012 (8)
C12	0.0483 (9)	0.0517 (10)	0.0488 (9)	0.0014 (7)	0.0032 (7)	0.0040 (7)
C13	0.0806 (15)	0.0761 (14)	0.0581 (12)	−0.0112 (11)	−0.0225 (10)	0.0095 (10)
C14	0.0432 (8)	0.0388 (8)	0.0408 (8)	0.0043 (6)	−0.0039 (6)	0.0010 (6)
C15	0.0566 (10)	0.0523 (10)	0.0425 (9)	−0.0013 (8)	−0.0036 (7)	0.0028 (7)
C16	0.0681 (12)	0.0584 (11)	0.0489 (10)	0.0040 (9)	−0.0161 (9)	−0.0086 (8)
C17	0.0570 (11)	0.0439 (10)	0.0800 (14)	−0.0070 (8)	−0.0058 (10)	−0.0063 (9)
C18	0.0711 (12)	0.0482 (10)	0.0755 (13)	−0.0109 (9)	0.0145 (10)	0.0017 (9)
C19	0.0651 (11)	0.0480 (9)	0.0475 (10)	−0.0006 (8)	0.0052 (8)	0.0003 (7)
C20	0.0396 (8)	0.0431 (8)	0.0429 (8)	0.0008 (6)	−0.0021 (6)	0.0016 (6)
C21	0.0442 (8)	0.0516 (9)	0.0474 (9)	0.0145 (7)	−0.0021 (7)	−0.0003 (7)
C22	0.0535 (9)	0.0570 (10)	0.0427 (9)	0.0163 (8)	0.0001 (7)	−0.0055 (7)
C23	0.0458 (8)	0.0488 (9)	0.0407 (8)	0.0091 (7)	−0.0041 (6)	0.0016 (7)
C24	0.0450 (9)	0.0550 (10)	0.0488 (9)	0.0161 (8)	−0.0026 (7)	−0.0037 (8)
C25	0.0482 (9)	0.0518 (10)	0.0458 (9)	0.0094 (7)	−0.0020 (7)	−0.0072 (7)
C26	0.0464 (9)	0.0547 (10)	0.0517 (10)	0.0109 (8)	−0.0064 (7)	0.0000 (8)
C27	0.0515 (10)	0.0570 (10)	0.0539 (11)	0.0114 (8)	−0.0068 (8)	0.0014 (8)
C28	0.0879 (16)	0.0896 (17)	0.0579 (14)	0.0258 (13)	−0.0137 (11)	0.0045 (12)

Geometric parameters (Å, º)

S1—C4	1.7412 (17)	C11—C12	1.390 (2)
S1—C5	1.7241 (17)	C12—H12	0.9500
F1—C17	1.359 (2)	C13—H13A	0.9800
O1—C23	1.3701 (19)	C13—H13B	0.9800
O1—C26	1.4243 (19)	C13—H13C	0.9800
N1—N2	1.3827 (17)	C14—C15	1.380 (2)
N1—C3	1.477 (2)	C14—C19	1.381 (2)
N1—C4	1.357 (2)	C15—H15	0.9500
N2—C1	1.294 (2)	C15—C16	1.390 (2)
N3—C4	1.3005 (19)	C16—H16	0.9500
N3—C6	1.388 (2)	C16—C17	1.364 (3)
C1—C2	1.503 (2)	C17—C18	1.364 (3)
C1—C20	1.462 (2)	C18—H18	0.9500
C2—H2A	0.9900	C18—C19	1.383 (3)
C2—H2B	0.9900	C19—H19	0.9500
C2—C3	1.545 (2)	C20—C21	1.395 (2)
C3—H3	1.0000	C20—C25	1.392 (2)
C3—C14	1.510 (2)	C21—H21	0.9500
C5—H5	0.9500	C21—C22	1.369 (2)
C5—C6	1.355 (2)	C22—H22	0.9500
C6—C7	1.478 (2)	C22—C23	1.395 (2)
C7—C8	1.383 (2)	C23—C24	1.380 (2)
C7—C12	1.384 (2)	C24—H24	0.9500
C8—H8	0.9500	C24—C25	1.390 (2)
C8—C9	1.386 (3)	C25—H25	0.9500
C9—H9	0.9500	C26—H26A	0.9900
C9—C10	1.373 (3)	C26—H26B	0.9900
C10—C11	1.378 (3)	C26—C27	1.454 (2)
C10—C13	1.513 (2)	C27—C28	1.170 (3)
C11—H11	0.9500	C28—H28	0.93 (3)
C5—S1—C4	87.87 (8)	C10—C13—H13B	109.5
C23—O1—C26	117.49 (13)	C10—C13—H13C	109.5
N2—N1—C3	114.19 (12)	H13A—C13—H13B	109.5
C4—N1—N2	119.95 (13)	H13A—C13—H13C	109.5
C4—N1—C3	124.26 (13)	H13B—C13—H13C	109.5
C1—N2—N1	107.90 (13)	C15—C14—C3	120.60 (15)
C4—N3—C6	109.84 (13)	C15—C14—C19	118.61 (15)
N2—C1—C2	113.90 (13)	C19—C14—C3	120.74 (14)
N2—C1—C20	121.29 (14)	C14—C15—H15	119.5
C20—C1—C2	124.81 (14)	C14—C15—C16	120.95 (17)
C1—C2—H2A	111.1	C16—C15—H15	119.5
C1—C2—H2B	111.1	C15—C16—H16	120.9
C1—C2—C3	103.20 (13)	C17—C16—C15	118.14 (17)
H2A—C2—H2B	109.1	C17—C16—H16	120.9
C3—C2—H2A	111.1	F1—C17—C16	118.16 (19)
C3—C2—H2B	111.1	F1—C17—C18	118.96 (19)
N1—C3—C2	100.79 (12)	C18—C17—C16	122.87 (17)
N1—C3—H3	109.8	C17—C18—H18	121.0
N1—C3—C14	112.32 (13)	C17—C18—C19	118.08 (18)
C2—C3—H3	109.8	C19—C18—H18	121.0
C14—C3—C2	114.04 (14)	C14—C19—C18	121.33 (17)
C14—C3—H3	109.8	C14—C19—H19	119.3
N1—C4—S1	121.16 (12)	C18—C19—H19	119.3
N3—C4—S1	116.01 (12)	C21—C20—C1	120.91 (14)
N3—C4—N1	122.82 (15)	C25—C20—C1	121.08 (14)
S1—C5—H5	124.4	C25—C20—C21	118.01 (14)
C6—C5—S1	111.16 (13)	C20—C21—H21	119.4
C6—C5—H5	124.4	C22—C21—C20	121.19 (15)
N3—C6—C7	117.90 (14)	C22—C21—H21	119.4
C5—C6—N3	115.10 (14)	C21—C22—H22	119.9
C5—C6—C7	126.98 (15)	C21—C22—C23	120.10 (15)
C8—C7—C6	121.59 (16)	C23—C22—H22	119.9
C8—C7—C12	117.46 (16)	O1—C23—C22	114.61 (14)
C12—C7—C6	120.92 (15)	O1—C23—C24	125.41 (14)
C7—C8—H8	119.6	C24—C23—C22	119.97 (15)
C7—C8—C9	120.82 (18)	C23—C24—H24	120.3
C9—C8—H8	119.6	C23—C24—C25	119.35 (15)
C8—C9—H9	119.0	C25—C24—H24	120.3
C10—C9—C8	122.04 (18)	C20—C25—H25	119.3
C10—C9—H9	119.0	C24—C25—C20	121.37 (15)
C9—C10—C11	117.13 (16)	C24—C25—H25	119.3
C9—C10—C13	120.92 (19)	O1—C26—H26A	110.4
C11—C10—C13	121.93 (19)	O1—C26—H26B	110.4
C10—C11—H11	119.2	O1—C26—C27	106.64 (14)
C10—C11—C12	121.54 (17)	H26A—C26—H26B	108.6
C12—C11—H11	119.2	C27—C26—H26A	110.4
C7—C12—C11	120.99 (16)	C27—C26—H26B	110.4
C7—C12—H12	119.5	C28—C27—C26	178.5 (2)
C11—C12—H12	119.5	C27—C28—H28	171.9 (19)
C10—C13—H13A	109.5
S1—C5—C6—N3	0.04 (19)	C4—N3—C6—C7	−177.89 (13)
S1—C5—C6—C7	178.66 (13)	C5—S1—C4—N1	−177.59 (15)
F1—C17—C18—C19	178.88 (18)	C5—S1—C4—N3	1.24 (13)
O1—C23—C24—C25	178.61 (17)	C5—C6—C7—C8	−12.2 (3)
N1—N2—C1—C2	0.80 (19)	C5—C6—C7—C12	170.00 (17)
N1—N2—C1—C20	−178.53 (14)	C6—N3—C4—S1	−1.41 (17)
N1—C3—C14—C15	129.54 (16)	C6—N3—C4—N1	177.40 (15)
N1—C3—C14—C19	−53.1 (2)	C6—C7—C8—C9	−177.19 (18)
N2—N1—C3—C2	1.52 (18)	C6—C7—C12—C11	177.95 (15)
N2—N1—C3—C14	123.29 (14)	C7—C8—C9—C10	−0.7 (4)
N2—N1—C4—S1	−4.6 (2)	C8—C7—C12—C11	0.0 (3)
N2—N1—C4—N3	176.69 (14)	C8—C9—C10—C11	0.0 (3)
N2—C1—C2—C3	0.14 (19)	C8—C9—C10—C13	178.8 (2)
N2—C1—C20—C21	−0.6 (2)	C9—C10—C11—C12	0.8 (3)
N2—C1—C20—C25	179.91 (16)	C10—C11—C12—C7	−0.8 (3)
N3—C6—C7—C8	166.41 (17)	C12—C7—C8—C9	0.7 (3)
N3—C6—C7—C12	−11.4 (2)	C13—C10—C11—C12	−178.06 (17)
C1—C2—C3—N1	−0.93 (16)	C14—C15—C16—C17	1.5 (3)
C1—C2—C3—C14	−121.48 (15)	C15—C14—C19—C18	0.1 (3)
C1—C20—C21—C22	179.82 (16)	C15—C16—C17—F1	−179.82 (17)
C1—C20—C25—C24	−179.47 (16)	C15—C16—C17—C18	−1.0 (3)
C2—C1—C20—C21	−179.83 (16)	C16—C17—C18—C19	0.0 (3)
C2—C1—C20—C25	0.7 (3)	C17—C18—C19—C14	0.4 (3)
C2—C3—C14—C15	−116.59 (17)	C19—C14—C15—C16	−1.1 (3)
C2—C3—C14—C19	60.7 (2)	C20—C1—C2—C3	179.44 (15)
C3—N1—N2—C1	−1.52 (19)	C20—C21—C22—C23	−0.2 (3)
C3—N1—C4—S1	−169.30 (12)	C21—C20—C25—C24	1.0 (3)
C3—N1—C4—N3	11.9 (3)	C21—C22—C23—O1	−178.37 (16)
C3—C14—C15—C16	176.31 (16)	C21—C22—C23—C24	0.7 (3)
C3—C14—C19—C18	−177.27 (17)	C22—C23—C24—C25	−0.3 (3)
C4—S1—C5—C6	−0.66 (14)	C23—O1—C26—C27	−168.80 (16)
C4—N1—N2—C1	−167.73 (15)	C23—C24—C25—C20	−0.5 (3)
C4—N1—C3—C2	167.05 (15)	C25—C20—C21—C22	−0.7 (3)
C4—N1—C3—C14	−71.2 (2)	C26—O1—C23—C22	179.37 (16)
C4—N3—C6—C5	0.9 (2)	C26—O1—C23—C24	0.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···N3	0.95	2.52	2.849 (2)	100
C16—H16···S1^i	0.95	3.10	3.9986 (19)	159
C21—H21···N2	0.95	2.55	2.853 (2)	99
C22—H22···F1^ii	0.95	2.53	3.245 (2)	132

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