3,5-Bis(4-fluoro-phen-yl)-1-phenyl-4,5-dihydro-1H-pyrazole.

In the title compound, C(21)H(16)F(2)N(2), the dihedral angle between the fluoro-phenyl groups is 66.34 (8)°, and the dihedral angle between the envelope-configured pyrazole group (N/N/C/C/C) and the benzene ring is 11.50 (9)°. The dihedral angles between the benzene and the two fluoro-substituted phenyl groups are 77.7 (6) and 16.7 (5)°. Weak C-H⋯π interactions contribute to the stability of the crystal structure.

Related literature

For background to the chemistry and biological activity of pyrazolines, see: Amir et al. (2008 ▶); Bhaskarreddy et al. (1997 ▶); Fustero et al. (2009 ▶); Hes et al. (1978 ▶); Klimova et al. (1999 ▶); Regaila et al. (1979 ▶); Sarojini et al. (2010 ▶); Wiley et al. (1958 ▶); Spek (2009 ▶). For related structures, see: Butcher et al. (2007 ▶); Fun, Quah et al. (2009 ▶); Fun, Yeap et al. (2009 ▶); Fun et al. (2010 ▶); Guo et al. (2006 ▶, 2007 ▶); Li (2007a ▶,b ▶); Loh et al. (2010 ▶); Yathirajan et al. (2007a ▶,b ▶).

Experimental

Crystal data

C21H16F2N2

M = 334.36

Monoclinic,

a = 12.2880 (3) Å

b = 13.1678 (3) Å

c = 11.3245 (3) Å

β = 112.661 (3)°

V = 1690.91 (7) Å3

Z = 4

Cu Kα radiation

μ = 0.77 mm−1

T = 100 K

0.28 × 0.24 × 0.23 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Ruby (Gemini Cu) detector

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T min = 0.774, T max = 1.000

7737 measured reflections

3541 independent reflections

2740 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.116

S = 1.05

3541 reflections

226 parameters

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.16 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; 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 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810026036/tk2686sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026036/tk2686Isup2.hkl

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

C21H16F2N2	F(000) = 696
Mr = 334.36	Dx = 1.313 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 3839 reflections
a = 12.2880 (3) Å	θ = 4.5–77.2°
b = 13.1678 (3) Å	µ = 0.77 mm−1
c = 11.3245 (3) Å	T = 100 K
β = 112.661 (3)°	Block, colorless
V = 1690.91 (7) Å3	0.28 × 0.24 × 0.23 mm
Z = 4

Oxford Diffraction Xcalibur diffractometer with a Ruby (Gemini Cu) detector	3541 independent reflections
Radiation source: fine-focus sealed tube	2740 reflections with I > 2σ(I)
graphite	Rint = 0.016
Detector resolution: 10.5081 pixels mm-1	θmax = 77.4°, θmin = 5.2°
ω scans	h = −11→15
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −16→14
Tmin = 0.774, Tmax = 1.000	l = −13→14
7737 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.060P)2 + 0.1618P] where P = (Fo2 + 2Fc2)/3
3541 reflections	(Δ/σ)max < 0.001
226 parameters	Δρmax = 0.15 e Å−3
0 restraints	Δρmin = −0.16 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
F1	0.14722 (10)	0.03973 (7)	0.26845 (11)	0.0891 (3)
F2	0.03475 (11)	0.92804 (9)	0.61215 (12)	0.0958 (4)
N1	0.27887 (10)	0.60196 (9)	0.37791 (11)	0.0583 (3)
N2	0.31295 (11)	0.50566 (9)	0.35601 (11)	0.0594 (3)
C1	0.11598 (14)	0.67082 (12)	0.57694 (14)	0.0649 (4)
H1	0.1090	0.6062	0.6064	0.078*
C2	0.06799 (15)	0.75266 (13)	0.61618 (15)	0.0710 (4)
H2	0.0288	0.7437	0.6712	0.085*
C3	0.07946 (15)	0.84700 (12)	0.57224 (15)	0.0682 (4)
C4	0.13479 (15)	0.86269 (12)	0.48921 (17)	0.0725 (4)
H4	0.1398	0.9276	0.4593	0.087*
C5	0.18302 (14)	0.78039 (12)	0.45068 (15)	0.0643 (4)
H5	0.2215	0.7902	0.3951	0.077*
C6	0.17452 (12)	0.68283 (10)	0.49427 (12)	0.0549 (3)
C7	0.22462 (12)	0.59450 (11)	0.45457 (12)	0.0554 (3)
C8	0.21469 (15)	0.48688 (11)	0.49360 (15)	0.0644 (4)
H8A	0.1353	0.4608	0.4505	0.077*
H8B	0.2374	0.4812	0.5854	0.077*
C9	0.30233 (13)	0.43192 (10)	0.44948 (13)	0.0563 (3)
H9	0.3785	0.4265	0.5218	0.068*
C10	0.26207 (11)	0.32735 (10)	0.39674 (12)	0.0515 (3)
C11	0.18963 (13)	0.31090 (11)	0.26960 (13)	0.0603 (3)
H11	0.1665	0.3654	0.2132	0.072*
C12	0.15145 (14)	0.21357 (13)	0.22594 (14)	0.0658 (4)
H12	0.1039	0.2020	0.1405	0.079*
C13	0.18527 (14)	0.13539 (11)	0.31124 (15)	0.0632 (4)
C14	0.25607 (15)	0.14782 (11)	0.43752 (15)	0.0662 (4)
H14	0.2775	0.0929	0.4934	0.079*
C15	0.29473 (14)	0.24498 (11)	0.47929 (14)	0.0605 (3)
H15	0.3437	0.2553	0.5646	0.073*
C16	0.39681 (12)	0.49799 (11)	0.30110 (13)	0.0567 (3)
C17	0.46147 (13)	0.40957 (13)	0.31169 (15)	0.0660 (4)
H17	0.4526	0.3556	0.3602	0.079*
C18	0.53935 (14)	0.40141 (15)	0.25016 (18)	0.0769 (5)
H18	0.5818	0.3417	0.2573	0.092*
C19	0.55439 (16)	0.48058 (17)	0.17879 (18)	0.0853 (5)
H19	0.6060	0.4745	0.1369	0.102*
C20	0.49212 (17)	0.56887 (17)	0.17010 (18)	0.0838 (5)
H20	0.5032	0.6231	0.1232	0.101*
C21	0.41337 (15)	0.57872 (13)	0.22966 (15)	0.0679 (4)
H21	0.3716	0.6389	0.2222	0.081*

	U11	U22	U33	U12	U13	U23
F1	0.1227 (8)	0.0572 (5)	0.1070 (7)	−0.0245 (5)	0.0660 (7)	−0.0303 (5)
F2	0.1130 (8)	0.0748 (7)	0.1084 (8)	0.0252 (6)	0.0524 (7)	−0.0023 (6)
N1	0.0659 (6)	0.0496 (6)	0.0595 (6)	−0.0020 (5)	0.0243 (5)	0.0031 (5)
N2	0.0710 (7)	0.0487 (6)	0.0649 (6)	−0.0046 (5)	0.0332 (6)	0.0029 (5)
C1	0.0796 (9)	0.0579 (8)	0.0594 (8)	0.0042 (7)	0.0292 (7)	0.0100 (6)
C2	0.0806 (10)	0.0748 (11)	0.0610 (8)	0.0123 (8)	0.0309 (7)	0.0080 (7)
C3	0.0734 (9)	0.0615 (9)	0.0660 (8)	0.0099 (7)	0.0226 (7)	−0.0019 (7)
C4	0.0819 (10)	0.0501 (8)	0.0846 (10)	0.0001 (7)	0.0310 (8)	0.0051 (7)
C5	0.0739 (9)	0.0559 (8)	0.0653 (8)	−0.0043 (7)	0.0294 (7)	0.0037 (6)
C6	0.0608 (7)	0.0511 (7)	0.0482 (6)	−0.0024 (6)	0.0160 (5)	0.0006 (5)
C7	0.0637 (7)	0.0505 (7)	0.0492 (6)	−0.0054 (6)	0.0186 (6)	0.0013 (5)
C8	0.0879 (10)	0.0489 (7)	0.0653 (8)	−0.0086 (7)	0.0392 (8)	−0.0038 (6)
C9	0.0655 (7)	0.0490 (7)	0.0521 (7)	−0.0080 (6)	0.0199 (6)	0.0009 (5)
C10	0.0568 (7)	0.0468 (6)	0.0521 (6)	−0.0041 (5)	0.0224 (5)	−0.0005 (5)
C11	0.0666 (8)	0.0574 (8)	0.0536 (7)	−0.0053 (6)	0.0193 (6)	0.0030 (6)
C12	0.0689 (8)	0.0707 (9)	0.0574 (8)	−0.0129 (7)	0.0238 (7)	−0.0140 (7)
C13	0.0790 (9)	0.0481 (7)	0.0783 (9)	−0.0110 (7)	0.0479 (8)	−0.0148 (7)
C14	0.0893 (10)	0.0472 (7)	0.0713 (9)	0.0007 (7)	0.0409 (8)	0.0036 (6)
C15	0.0748 (8)	0.0518 (7)	0.0532 (7)	−0.0019 (6)	0.0229 (6)	0.0018 (6)
C16	0.0554 (7)	0.0578 (8)	0.0543 (7)	−0.0101 (6)	0.0183 (6)	−0.0038 (6)
C17	0.0608 (7)	0.0643 (9)	0.0730 (9)	−0.0073 (7)	0.0260 (7)	0.0002 (7)
C18	0.0634 (8)	0.0789 (11)	0.0888 (11)	−0.0029 (8)	0.0296 (8)	−0.0106 (9)
C19	0.0762 (10)	0.1065 (15)	0.0854 (11)	−0.0113 (10)	0.0445 (9)	−0.0060 (11)
C20	0.0886 (11)	0.0945 (13)	0.0772 (11)	−0.0122 (10)	0.0420 (9)	0.0117 (9)
C21	0.0735 (9)	0.0678 (9)	0.0649 (8)	−0.0065 (7)	0.0295 (7)	0.0055 (7)

F1—C13	1.3658 (16)	C9—H9	0.9800
F2—C3	1.3551 (19)	C10—C15	1.3865 (19)
N1—C7	1.2859 (19)	C10—C11	1.3873 (19)
N1—N2	1.3875 (17)	C11—C12	1.389 (2)
N2—C16	1.3973 (19)	C11—H11	0.9300
N2—C9	1.4787 (17)	C12—C13	1.363 (2)
C1—C2	1.382 (2)	C12—H12	0.9300
C1—C6	1.392 (2)	C13—C14	1.367 (2)
C1—H1	0.9300	C14—C15	1.383 (2)
C2—C3	1.366 (2)	C14—H14	0.9300
C2—H2	0.9300	C15—H15	0.9300
C3—C4	1.372 (3)	C16—C17	1.388 (2)
C4—C5	1.384 (2)	C16—C21	1.398 (2)
C4—H4	0.9300	C17—C18	1.388 (2)
C5—C6	1.395 (2)	C17—H17	0.9300
C5—H5	0.9300	C18—C19	1.374 (3)
C6—C7	1.465 (2)	C18—H18	0.9300
C7—C8	1.503 (2)	C19—C20	1.374 (3)
C8—C9	1.532 (2)	C19—H19	0.9300
C8—H8A	0.9700	C20—C21	1.382 (3)
C8—H8B	0.9700	C20—H20	0.9300
C9—C10	1.5066 (18)	C21—H21	0.9300
C7—N1—N2	108.75 (11)	C15—C10—C11	118.74 (13)
N1—N2—C16	118.08 (11)	C15—C10—C9	118.83 (12)
N1—N2—C9	110.87 (11)	C11—C10—C9	122.38 (12)
C16—N2—C9	123.69 (12)	C10—C11—C12	120.48 (13)
C2—C1—C6	121.53 (15)	C10—C11—H11	119.8
C2—C1—H1	119.2	C12—C11—H11	119.8
C6—C1—H1	119.2	C13—C12—C11	118.43 (13)
C3—C2—C1	118.40 (16)	C13—C12—H12	120.8
C3—C2—H2	120.8	C11—C12—H12	120.8
C1—C2—H2	120.8	C12—C13—F1	118.43 (14)
F2—C3—C2	118.86 (16)	C12—C13—C14	123.25 (13)
F2—C3—C4	118.80 (15)	F1—C13—C14	118.31 (14)
C2—C3—C4	122.34 (15)	C13—C14—C15	117.69 (14)
C3—C4—C5	118.93 (15)	C13—C14—H14	121.2
C3—C4—H4	120.5	C15—C14—H14	121.2
C5—C4—H4	120.5	C14—C15—C10	121.40 (13)
C4—C5—C6	120.67 (15)	C14—C15—H15	119.3
C4—C5—H5	119.7	C10—C15—H15	119.3
C6—C5—H5	119.7	C17—C16—N2	121.18 (13)
C1—C6—C5	118.12 (14)	C17—C16—C21	118.80 (14)
C1—C6—C7	120.21 (13)	N2—C16—C21	119.97 (14)
C5—C6—C7	121.67 (13)	C18—C17—C16	120.26 (16)
N1—C7—C6	122.33 (13)	C18—C17—H17	119.9
N1—C7—C8	113.11 (13)	C16—C17—H17	119.9
C6—C7—C8	124.52 (13)	C19—C18—C17	120.75 (18)
C7—C8—C9	101.68 (12)	C19—C18—H18	119.6
C7—C8—H8A	111.4	C17—C18—H18	119.6
C9—C8—H8A	111.4	C20—C19—C18	119.11 (17)
C7—C8—H8B	111.4	C20—C19—H19	120.4
C9—C8—H8B	111.4	C18—C19—H19	120.4
H8A—C8—H8B	109.3	C19—C20—C21	121.30 (17)
N2—C9—C10	114.99 (11)	C19—C20—H20	119.4
N2—C9—C8	100.96 (11)	C21—C20—H20	119.4
C10—C9—C8	113.34 (11)	C20—C21—C16	119.77 (17)
N2—C9—H9	109.1	C20—C21—H21	120.1
C10—C9—H9	109.1	C16—C21—H21	120.1
C8—C9—H9	109.1
C7—N1—N2—C16	−164.89 (12)	N2—C9—C10—C15	153.43 (13)
C7—N1—N2—C9	−13.70 (16)	C8—C9—C10—C15	−91.13 (16)
C6—C1—C2—C3	−0.2 (2)	N2—C9—C10—C11	−29.19 (19)
C1—C2—C3—F2	−178.70 (14)	C8—C9—C10—C11	86.26 (17)
C1—C2—C3—C4	1.2 (3)	C15—C10—C11—C12	−0.5 (2)
F2—C3—C4—C5	178.47 (14)	C9—C10—C11—C12	−177.88 (13)
C2—C3—C4—C5	−1.4 (3)	C10—C11—C12—C13	1.0 (2)
C3—C4—C5—C6	0.7 (2)	C11—C12—C13—F1	179.67 (13)
C2—C1—C6—C5	−0.5 (2)	C11—C12—C13—C14	−0.8 (2)
C2—C1—C6—C7	179.91 (14)	C12—C13—C14—C15	−0.1 (2)
C4—C5—C6—C1	0.2 (2)	F1—C13—C14—C15	179.47 (14)
C4—C5—C6—C7	179.85 (14)	C13—C14—C15—C10	0.7 (2)
N2—N1—C7—C6	−178.39 (12)	C11—C10—C15—C14	−0.4 (2)
N2—N1—C7—C8	−0.60 (16)	C9—C10—C15—C14	177.09 (14)
C1—C6—C7—N1	179.65 (13)	N1—N2—C16—C17	160.01 (13)
C5—C6—C7—N1	0.0 (2)	C9—N2—C16—C17	12.8 (2)
C1—C6—C7—C8	2.1 (2)	N1—N2—C16—C21	−22.60 (19)
C5—C6—C7—C8	−177.51 (14)	C9—N2—C16—C21	−169.85 (13)
N1—C7—C8—C9	13.51 (16)	N2—C16—C17—C18	176.23 (14)
C6—C7—C8—C9	−168.75 (12)	C21—C16—C17—C18	−1.2 (2)
N1—N2—C9—C10	143.41 (12)	C16—C17—C18—C19	0.5 (2)
C16—N2—C9—C10	−67.31 (17)	C17—C18—C19—C20	0.7 (3)
N1—N2—C9—C8	21.03 (14)	C18—C19—C20—C21	−1.2 (3)
C16—N2—C9—C8	170.31 (12)	C19—C20—C21—C16	0.5 (3)
C7—C8—C9—N2	−19.28 (13)	C17—C16—C21—C20	0.7 (2)
C7—C8—C9—C10	−142.80 (12)	N2—C16—C21—C20	−176.72 (15)

X–H···CgX (Å)	X···Cg, (Å)	H···Cg	X···Perp (Å)
C9–H9···Cg4i	3.6677 (16)	2.82	2.76
C12–H12···Cg22	3.6061 (18)	2.88	-2.79

Table 1

Y—X⋯Cg π ring inter­actions (Å, °)

Cg4 is the centroid of ring C16–C21 and Cg2 is the centroid of the ring C1–C6.

X—H⋯CgX	X⋯Cg	H⋯Cg	X⋯Perp
C9—H9⋯Cg4i	3.6677 (16)	2.82	2.76
C12—H12⋯Cg2ii	3.6061 (18)	2.88	−2.79

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