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

In the title compound, C(21)H(16)BrFN(2), the fluoro-substituted benzene ring is disordered over two orientations about the C-F bond and the C-C bond between the benzene and pyrazole groups with a site-occupancy ratio of 0.516 (8):0.484 (8). The central pyrazole ring [maximum deviation = 0.035 (3) Å] makes dihedral angles of 22.4 (2), 11.0 (2), 77.19 (16) and 7.44 (17)° with the two disorder components of the benzene ring, the bromo-substituted benzene ring and the phenyl ring, respectively. In the crystal, mol-ecules are linked into a layer parallel to the bc plane through C-H⋯π inter-actions.

Related literature

For background to pyrazoline derivatives, see: Fun et al. (2010 ▶); Samshuddin et al. (2010 ▶, 2011 ▶). For a related structure, see: Samshuddin et al. (2010 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C21H16BrFN2

M = 395.27

Monoclinic,

a = 20.5345 (5) Å

b = 5.2689 (1) Å

c = 16.1929 (5) Å

β = 104.443 (2)°

V = 1696.61 (7) Å3

Z = 4

Mo Kα radiation

μ = 2.44 mm−1

T = 100 K

0.25 × 0.13 × 0.09 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.583, T max = 0.818

16716 measured reflections

4974 independent reflections

3761 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.113

S = 1.01

4974 reflections

263 parameters

130 restraints

H-atom parameters constrained

Δρmax = 1.26 e Å−3

Δρmin = −0.99 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 datablock(s) global, I. DOI: 10.1107/S160053681203454X/is5174sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681203454X/is5174Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681203454X/is5174Isup3.cml

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

C21H16BrFN2	F(000) = 800
Mr = 395.27	Dx = 1.547 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4161 reflections
a = 20.5345 (5) Å	θ = 2.9–30.0°
b = 5.2689 (1) Å	µ = 2.44 mm−1
c = 16.1929 (5) Å	T = 100 K
β = 104.443 (2)°	Block, orange
V = 1696.61 (7) Å3	0.25 × 0.13 × 0.09 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	4974 independent reflections
Radiation source: fine-focus sealed tube	3761 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
φ and ω scans	θmax = 30.2°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −29→28
Tmin = 0.583, Tmax = 0.818	k = −7→7
16716 measured reflections	l = −20→22

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0403P)2 + 3.9007P] where P = (Fo2 + 2Fc2)/3
4974 reflections	(Δ/σ)max = 0.001
263 parameters	Δρmax = 1.26 e Å−3
130 restraints	Δρmin = −0.99 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	Occ. (<1)
Br1	0.438172 (16)	0.29092 (7)	0.31781 (2)	0.02527 (11)
F1	1.03501 (11)	1.0361 (5)	0.31750 (17)	0.0482 (7)
N1	0.76496 (13)	0.5313 (5)	0.52597 (18)	0.0205 (6)
N2	0.82467 (12)	0.5535 (5)	0.50180 (17)	0.0189 (5)
C1	0.58983 (16)	0.7495 (6)	0.4593 (2)	0.0198 (6)
H1A	0.5930	0.8942	0.4951	0.024*
C2	0.52691 (16)	0.6511 (6)	0.4199 (2)	0.0210 (7)
H2A	0.4872	0.7281	0.4282	0.025*
C3	0.52306 (15)	0.4394 (6)	0.3684 (2)	0.0194 (6)
C4	0.58002 (16)	0.3298 (6)	0.3531 (2)	0.0212 (6)
H4A	0.5765	0.1866	0.3166	0.025*
C5	0.64254 (16)	0.4316 (6)	0.3919 (2)	0.0202 (6)
H5A	0.6819	0.3593	0.3808	0.024*
C6	0.64832 (15)	0.6383 (6)	0.4469 (2)	0.0175 (6)
C7	0.71689 (15)	0.7394 (6)	0.4928 (2)	0.0184 (6)
H7A	0.7125	0.8523	0.5408	0.022*
C8	0.75404 (15)	0.8818 (6)	0.4346 (2)	0.0193 (6)
H8A	0.7292	0.8694	0.3740	0.023*
H8B	0.7606	1.0630	0.4508	0.023*
C9	0.82035 (15)	0.7440 (6)	0.4509 (2)	0.0183 (6)
C10	0.76131 (15)	0.3686 (6)	0.59269 (19)	0.0171 (6)
C11	0.81265 (15)	0.1909 (6)	0.6237 (2)	0.0202 (6)
H11A	0.8515	0.1880	0.6020	0.024*
C12	0.80621 (16)	0.0197 (6)	0.6863 (2)	0.0232 (7)
H12A	0.8408	−0.1014	0.7068	0.028*
C13	0.75020 (17)	0.0222 (7)	0.7196 (2)	0.0237 (7)
H13A	0.7461	−0.0966	0.7621	0.028*
C14	0.70032 (16)	0.2001 (7)	0.6900 (2)	0.0238 (7)
H14A	0.6620	0.2038	0.7129	0.029*
C15	0.70535 (16)	0.3739 (6)	0.6272 (2)	0.0213 (6)
H15A	0.6708	0.4958	0.6078	0.026*
C16	0.87551 (16)	0.8212 (6)	0.4136 (2)	0.0228 (7)
C19	0.98129 (18)	0.9645 (7)	0.3479 (2)	0.0333 (8)
C17	0.8674 (3)	0.9700 (12)	0.3440 (4)	0.0143 (13)	0.516 (8)
H17A	0.8232	1.0218	0.3153	0.017*	0.516 (8)
C18	0.9209 (4)	1.0507 (15)	0.3126 (5)	0.0138 (14)	0.516 (8)
H18A	0.9139	1.1664	0.2662	0.017*	0.516 (8)
C20	0.9970 (4)	0.8198 (14)	0.4250 (5)	0.0348 (17)	0.516 (8)
H20A	1.0420	0.7748	0.4526	0.042*	0.516 (8)
C21	0.9429 (3)	0.7482 (13)	0.4575 (5)	0.0287 (16)	0.516 (8)
H21A	0.9505	0.6513	0.5085	0.034*	0.516 (8)
C17X	0.8755 (4)	1.0417 (15)	0.3726 (4)	0.0186 (15)	0.484 (8)
H17B	0.8387	1.1544	0.3684	0.022*	0.484 (8)
C18X	0.9274 (5)	1.1126 (19)	0.3360 (5)	0.0211 (17)	0.484 (8)
H18B	0.9243	1.2636	0.3031	0.025*	0.484 (8)
C20X	0.9841 (3)	0.7160 (14)	0.3859 (4)	0.0226 (14)	0.484 (8)
H20B	1.0210	0.6052	0.3878	0.027*	0.484 (8)
C21X	0.9309 (3)	0.6444 (14)	0.4195 (4)	0.0200 (14)	0.484 (8)
H21B	0.9307	0.4834	0.4458	0.024*	0.484 (8)

	U11	U22	U33	U12	U13	U23
Br1	0.01981 (15)	0.03041 (18)	0.02509 (18)	−0.00327 (13)	0.00464 (12)	−0.00043 (15)
F1	0.0264 (11)	0.0682 (17)	0.0583 (16)	0.0129 (11)	0.0263 (11)	0.0328 (14)
N1	0.0165 (12)	0.0241 (14)	0.0221 (14)	0.0036 (10)	0.0071 (11)	0.0078 (11)
N2	0.0164 (11)	0.0212 (14)	0.0202 (14)	0.0005 (10)	0.0064 (10)	0.0037 (11)
C1	0.0255 (15)	0.0129 (16)	0.0224 (15)	0.0022 (11)	0.0084 (13)	−0.0011 (12)
C2	0.0204 (14)	0.0199 (16)	0.0258 (17)	0.0022 (11)	0.0114 (13)	0.0010 (13)
C3	0.0180 (13)	0.0225 (16)	0.0182 (15)	−0.0019 (11)	0.0051 (12)	0.0032 (13)
C4	0.0254 (15)	0.0202 (17)	0.0179 (15)	0.0027 (12)	0.0050 (12)	−0.0005 (12)
C5	0.0201 (14)	0.0223 (16)	0.0182 (15)	0.0072 (12)	0.0050 (12)	0.0003 (12)
C6	0.0192 (14)	0.0164 (14)	0.0174 (15)	0.0020 (11)	0.0057 (12)	0.0026 (11)
C7	0.0182 (13)	0.0170 (16)	0.0198 (15)	0.0027 (11)	0.0043 (12)	0.0004 (12)
C8	0.0207 (14)	0.0174 (14)	0.0209 (16)	0.0019 (11)	0.0073 (12)	0.0021 (12)
C9	0.0192 (13)	0.0164 (16)	0.0193 (15)	0.0014 (11)	0.0048 (12)	0.0010 (12)
C10	0.0183 (13)	0.0182 (14)	0.0132 (14)	−0.0042 (11)	0.0008 (11)	0.0002 (11)
C11	0.0168 (13)	0.0219 (15)	0.0203 (15)	−0.0022 (12)	0.0017 (12)	0.0010 (13)
C12	0.0214 (15)	0.0212 (16)	0.0233 (17)	−0.0021 (12)	−0.0015 (13)	0.0038 (13)
C13	0.0279 (16)	0.0258 (17)	0.0165 (16)	−0.0049 (13)	0.0039 (13)	0.0062 (13)
C14	0.0247 (15)	0.0282 (17)	0.0197 (16)	−0.0057 (13)	0.0082 (13)	0.0009 (14)
C15	0.0218 (14)	0.0231 (16)	0.0193 (16)	0.0006 (12)	0.0055 (13)	0.0012 (13)
C16	0.0207 (14)	0.0230 (16)	0.0251 (16)	0.0023 (12)	0.0066 (12)	0.0045 (13)
C19	0.0246 (16)	0.042 (2)	0.038 (2)	0.0051 (15)	0.0157 (15)	0.0160 (17)
C17	0.011 (2)	0.022 (3)	0.007 (3)	−0.002 (2)	−0.004 (2)	0.002 (2)
C18	0.015 (3)	0.020 (4)	0.005 (3)	−0.004 (2)	0.000 (3)	−0.001 (2)
C20	0.023 (3)	0.041 (4)	0.040 (4)	0.003 (3)	0.005 (3)	0.014 (3)
C21	0.026 (3)	0.033 (4)	0.028 (3)	0.003 (3)	0.006 (3)	0.012 (3)
C17X	0.018 (3)	0.018 (3)	0.019 (4)	0.001 (3)	0.004 (3)	0.000 (3)
C18X	0.026 (3)	0.022 (4)	0.013 (4)	−0.004 (3)	0.001 (3)	0.000 (3)
C20X	0.022 (3)	0.026 (3)	0.020 (3)	0.001 (3)	0.006 (2)	−0.005 (3)
C21X	0.027 (3)	0.020 (3)	0.014 (3)	−0.001 (2)	0.005 (2)	−0.005 (2)

Br1—C3	1.900 (3)	C12—C13	1.386 (5)
F1—C19	1.368 (4)	C12—H12A	0.9500
N1—N2	1.382 (3)	C13—C14	1.383 (5)
N1—C10	1.395 (4)	C13—H13A	0.9500
N1—C7	1.484 (4)	C14—C15	1.391 (5)
N2—C9	1.288 (4)	C14—H14A	0.9500
C1—C2	1.391 (5)	C15—H15A	0.9500
C1—C6	1.395 (4)	C16—C17X	1.338 (9)
C1—H1A	0.9500	C16—C17	1.349 (8)
C2—C3	1.383 (5)	C16—C21	1.441 (7)
C2—H2A	0.9500	C16—C21X	1.454 (7)
C3—C4	1.381 (4)	C19—C18	1.310 (9)
C4—C5	1.389 (4)	C19—C18X	1.328 (11)
C4—H4A	0.9500	C19—C20	1.429 (8)
C5—C6	1.393 (4)	C19—C20X	1.442 (8)
C5—H5A	0.9500	C17—C18	1.389 (9)
C6—C7	1.516 (4)	C17—H17A	0.9500
C7—C8	1.546 (4)	C18—H18A	0.9500
C7—H7A	1.0000	C20—C21	1.395 (9)
C8—C9	1.507 (4)	C20—H20A	0.9500
C8—H8A	0.9900	C21—H21A	0.9500
C8—H8B	0.9900	C17X—C18X	1.394 (10)
C9—C16	1.467 (4)	C17X—H17B	0.9500
C10—C15	1.398 (4)	C18X—H18B	0.9500
C10—C11	1.406 (4)	C20X—C21X	1.389 (9)
C11—C12	1.388 (5)	C20X—H20B	0.9500
C11—H11A	0.9500	C21X—H21B	0.9500
N2—N1—C10	119.6 (2)	C12—C13—H13A	120.4
N2—N1—C7	113.1 (2)	C13—C14—C15	121.1 (3)
C10—N1—C7	125.1 (3)	C13—C14—H14A	119.5
C9—N2—N1	108.8 (2)	C15—C14—H14A	119.5
C2—C1—C6	120.8 (3)	C14—C15—C10	119.8 (3)
C2—C1—H1A	119.6	C14—C15—H15A	120.1
C6—C1—H1A	119.6	C10—C15—H15A	120.1
C3—C2—C1	118.9 (3)	C17X—C16—C21	110.9 (4)
C3—C2—H2A	120.5	C17—C16—C21	118.1 (5)
C1—C2—H2A	120.5	C17X—C16—C21X	119.5 (5)
C4—C3—C2	121.5 (3)	C17—C16—C21X	111.1 (4)
C4—C3—Br1	118.5 (2)	C17X—C16—C9	122.7 (4)
C2—C3—Br1	120.0 (2)	C17—C16—C9	123.9 (4)
C3—C4—C5	119.1 (3)	C21—C16—C9	117.9 (4)
C3—C4—H4A	120.5	C21X—C16—C9	117.8 (4)
C5—C4—H4A	120.5	C18—C19—F1	120.5 (5)
C4—C5—C6	120.9 (3)	C18X—C19—F1	120.2 (5)
C4—C5—H5A	119.6	C18—C19—C20	123.3 (5)
C6—C5—H5A	119.6	C18X—C19—C20	116.0 (5)
C5—C6—C1	118.8 (3)	F1—C19—C20	115.8 (4)
C5—C6—C7	120.6 (3)	C18—C19—C20X	115.7 (5)
C1—C6—C7	120.6 (3)	C18X—C19—C20X	122.6 (6)
N1—C7—C6	111.7 (2)	F1—C19—C20X	117.0 (4)
N1—C7—C8	101.2 (2)	C16—C17—C18	122.7 (6)
C6—C7—C8	114.3 (3)	C16—C17—H17A	118.7
N1—C7—H7A	109.8	C18—C17—H17A	118.7
C6—C7—H7A	109.8	C19—C18—C17	118.9 (7)
C8—C7—H7A	109.8	C19—C18—H18A	120.6
C9—C8—C7	102.8 (2)	C17—C18—H18A	120.6
C9—C8—H8A	111.2	C21—C20—C19	116.5 (6)
C7—C8—H8A	111.2	C21—C20—H20A	121.7
C9—C8—H8B	111.2	C19—C20—H20A	121.7
C7—C8—H8B	111.2	C20—C21—C16	119.9 (6)
H8A—C8—H8B	109.1	C20—C21—H21A	120.0
N2—C9—C16	122.8 (3)	C16—C21—H21A	120.0
N2—C9—C8	113.7 (3)	C16—C17X—C18X	122.6 (7)
C16—C9—C8	123.4 (3)	C16—C17X—H17B	118.7
N1—C10—C15	120.4 (3)	C18X—C17X—H17B	118.7
N1—C10—C11	120.4 (3)	C19—C18X—C17X	118.6 (8)
C15—C10—C11	119.2 (3)	C19—C18X—H18B	120.7
C12—C11—C10	119.7 (3)	C17X—C18X—H18B	120.7
C12—C11—H11A	120.2	C21X—C20X—C19	117.5 (6)
C10—C11—H11A	120.2	C21X—C20X—H20B	121.2
C13—C12—C11	121.1 (3)	C19—C20X—H20B	121.2
C13—C12—H12A	119.4	C20X—C21X—C16	118.6 (6)
C11—C12—H12A	119.4	C20X—C21X—H21B	120.7
C14—C13—C12	119.1 (3)	C16—C21X—H21B	120.7
C14—C13—H13A	120.4
C10—N1—N2—C9	−168.5 (3)	C8—C9—C16—C17	−19.9 (5)
C7—N1—N2—C9	−4.5 (4)	N2—C9—C16—C21	−23.3 (5)
C6—C1—C2—C3	0.4 (5)	C8—C9—C16—C21	155.5 (4)
C1—C2—C3—C4	−2.2 (5)	N2—C9—C16—C21X	13.7 (5)
C1—C2—C3—Br1	177.1 (2)	C8—C9—C16—C21X	−167.4 (4)
C2—C3—C4—C5	1.4 (5)	C17X—C16—C17—C18	80.8 (12)
Br1—C3—C4—C5	−177.9 (2)	C21—C16—C17—C18	1.2 (4)
C3—C4—C5—C6	1.3 (5)	C21X—C16—C17—C18	−33.9 (4)
C4—C5—C6—C1	−3.0 (5)	C9—C16—C17—C18	176.7 (4)
C4—C5—C6—C7	176.6 (3)	C18X—C19—C18—C17	−85.6 (19)
C2—C1—C6—C5	2.2 (5)	F1—C19—C18—C17	178.7 (4)
C2—C1—C6—C7	−177.5 (3)	C20—C19—C18—C17	−9.2 (6)
N2—N1—C7—C6	128.1 (3)	C20X—C19—C18—C17	28.6 (6)
C10—N1—C7—C6	−69.1 (4)	C16—C17—C18—C19	5.1 (6)
N2—N1—C7—C8	6.1 (3)	C18—C19—C20—C21	6.8 (6)
C10—N1—C7—C8	168.9 (3)	C18X—C19—C20—C21	30.2 (7)
C5—C6—C7—N1	−42.2 (4)	F1—C19—C20—C21	179.2 (5)
C1—C6—C7—N1	137.4 (3)	C20X—C19—C20—C21	−80.2 (8)
C5—C6—C7—C8	71.9 (4)	C19—C20—C21—C16	−0.2 (7)
C1—C6—C7—C8	−108.4 (3)	C17X—C16—C21—C20	−30.3 (6)
N1—C7—C8—C9	−5.0 (3)	C17—C16—C21—C20	−3.5 (6)
C6—C7—C8—C9	−125.3 (3)	C21X—C16—C21—C20	82.0 (8)
N1—N2—C9—C16	179.7 (3)	C9—C16—C21—C20	−179.3 (4)
N1—N2—C9—C8	0.7 (4)	C17—C16—C17X—C18X	−77.7 (12)
C7—C8—C9—N2	3.0 (4)	C21—C16—C17X—C18X	34.0 (5)
C7—C8—C9—C16	−175.9 (3)	C21X—C16—C17X—C18X	−1.0 (4)
N2—N1—C10—C15	169.6 (3)	C9—C16—C17X—C18X	−178.8 (4)
C7—N1—C10—C15	7.7 (5)	C18—C19—C18X—C17X	87.1 (19)
N2—N1—C10—C11	−12.9 (4)	F1—C19—C18X—C17X	−175.8 (4)
C7—N1—C10—C11	−174.7 (3)	C20—C19—C18X—C17X	−28.3 (6)
N1—C10—C11—C12	−175.9 (3)	C20X—C19—C18X—C17X	9.7 (6)
C15—C10—C11—C12	1.7 (5)	C16—C17X—C18X—C19	−5.4 (6)
C10—C11—C12—C13	−0.7 (5)	C18—C19—C20X—C21X	−30.8 (6)
C11—C12—C13—C14	−0.5 (5)	C18X—C19—C20X—C21X	−7.4 (6)
C12—C13—C14—C15	0.6 (5)	F1—C19—C20X—C21X	177.9 (4)
C13—C14—C15—C10	0.5 (5)	C20—C19—C20X—C21X	81.3 (8)
N1—C10—C15—C14	176.0 (3)	C19—C20X—C21X—C16	0.8 (6)
C11—C10—C15—C14	−1.6 (5)	C17X—C16—C21X—C20X	3.1 (5)
N2—C9—C16—C17X	−168.4 (4)	C17—C16—C21X—C20X	29.6 (5)
C8—C9—C16—C17X	10.4 (5)	C21—C16—C21X—C20X	−79.9 (8)
N2—C9—C16—C17	161.2 (4)	C9—C16—C21X—C20X	−178.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···Cg1i	1.00	2.60	3.522 (3)	153
C17—H17A···Cg1ii	0.95	2.99	3.752 (6)	138

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C10–C15 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯Cg1i	1.00	2.60	3.522 (3)	153
C17—H17A⋯Cg1ii	0.95	2.99	3.752 (6)	138

Symmetry codes: (i) ; (ii) .