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

In the title compound, C(21)H(16)Br(2)N(2), the central pyrazole ring adopts an flattened envelope conformation, with the stereogenic C atom in the flap position. The deviations from planarity for this ring are relatively minor (r.m.s. deviation = 0.045 Å) and the dihedral angles formed with the N- and C(imine)-bound benzene rings are 7.73 (13) and 11.00 (13)°, respectively. By contrast, the benzene ring bound at the chiral C atom is almost orthogonal to the rest of the mol-ecule; the dihedral angle formed between this ring and the pyrazole ring is 79.53 (13)°. In the crystal, the packing is stabilized by C-H⋯N and C-H⋯Br inter-actions.

Related literature

For the pharmacological activity of pyrazoline derivatives, see: Hes et al. (1978 ▶); Amir et al. (2008 ▶); Sarojini et al. (2010 ▶). For related structures, see: Fun et al. (2010 ▶); Yathirajan et al. (2007 ▶). For the structure of the parent compound, 1,3,5-triphenyl-2-pyrazoline, see: Foces-Foces et al. (2001 ▶). For conformational analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C21H16Br2N2

M = 456.18

Orthorhombic,

a = 10.5815 (3) Å

b = 11.2119 (3) Å

c = 15.4569 (4) Å

V = 1833.79 (9) Å3

Z = 4

Mo Kα radiation

μ = 4.43 mm−1

T = 100 K

0.35 × 0.15 × 0.08 mm

Data collection

Bruker SMART APEX diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.537, T max = 0.746

17504 measured reflections

4201 independent reflections

3753 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.052

S = 1.02

4201 reflections

226 parameters

H-atom parameters constrained

Δρmax = 0.60 e Å−3

Δρmin = −0.40 e Å−3

Absolute structure: Flack (1983 ▶), 1804 Friedel pairs

Flack parameter: 0.003 (7)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810015795/hb5428sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015795/hb5428Isup2.hkl

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

C21H16Br2N2	F(000) = 904
Mr = 456.18	Dx = 1.652 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4444 reflections
a = 10.5815 (3) Å	θ = 2.3–26.2°
b = 11.2119 (3) Å	µ = 4.43 mm−1
c = 15.4569 (4) Å	T = 100 K
V = 1833.79 (9) Å3	Block, yellow
Z = 4	0.35 × 0.15 × 0.08 mm

Bruker SMART APEX diffractometer	4201 independent reflections
Radiation source: fine-focus sealed tube	3753 reflections with I > 2σ(I)
graphite	Rint = 0.044
ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.537, Tmax = 0.746	k = −14→14
17504 measured reflections	l = −20→20

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)] = 0.027	H-atom parameters constrained
wR(F2) = 0.052	w = 1/[σ2(Fo2) + (0.0105P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
4201 reflections	Δρmax = 0.60 e Å−3
226 parameters	Δρmin = −0.40 e Å−3
0 restraints	Absolute structure: Flack (1983), 1804 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.003 (7)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.45694 (3)	0.39983 (2)	−0.095975 (18)	0.03237 (9)
Br2	1.28094 (3)	−0.06644 (3)	0.379191 (19)	0.02784 (8)
N1	0.68637 (18)	−0.10495 (19)	0.19763 (12)	0.0155 (5)
N2	0.56377 (19)	−0.07418 (19)	0.18013 (13)	0.0175 (5)
C1	0.5321 (3)	0.0486 (2)	0.20739 (15)	0.0184 (5)
H1	0.4556	0.0479	0.2453	0.022*
C2	0.6507 (2)	0.0809 (3)	0.26139 (16)	0.0226 (6)
H2A	0.6878	0.1576	0.2422	0.027*
H2B	0.6304	0.0859	0.3238	0.027*
C3	0.7385 (2)	−0.0217 (2)	0.24286 (16)	0.0144 (6)
C4	0.5117 (2)	0.1321 (2)	0.13185 (17)	0.0165 (6)
C5	0.4266 (3)	0.2261 (2)	0.13916 (17)	0.0206 (6)
H5	0.3790	0.2351	0.1909	0.025*
C6	0.4100 (3)	0.3064 (2)	0.07249 (17)	0.0230 (6)
H6	0.3521	0.3707	0.0781	0.028*
C7	0.4791 (3)	0.2917 (2)	−0.00225 (17)	0.0208 (6)
C8	0.5631 (3)	0.1994 (2)	−0.01219 (16)	0.0213 (6)
H8	0.6087	0.1901	−0.0647	0.026*
C9	0.5803 (2)	0.1200 (2)	0.05566 (17)	0.0193 (6)
H9	0.6394	0.0567	0.0500	0.023*
C10	0.8685 (2)	−0.0309 (2)	0.27394 (16)	0.0141 (6)
C11	0.9485 (3)	−0.1218 (2)	0.24481 (16)	0.0179 (6)
H11	0.9182	−0.1784	0.2041	0.021*
C12	1.0714 (3)	−0.1300 (2)	0.27476 (17)	0.0199 (6)
H12	1.1256	−0.1914	0.2544	0.024*
C13	1.1146 (2)	−0.0478 (3)	0.33476 (17)	0.0190 (6)
C14	1.0378 (2)	0.0425 (2)	0.36482 (16)	0.0190 (5)
H14	1.0685	0.0981	0.4062	0.023*
C15	0.9159 (2)	0.0512 (2)	0.33413 (16)	0.0178 (6)
H15	0.8631	0.1140	0.3541	0.021*
C16	0.4888 (2)	−0.1457 (2)	0.12849 (16)	0.0168 (5)
C17	0.3627 (2)	−0.1161 (2)	0.11246 (16)	0.0195 (6)
H17	0.3271	−0.0468	0.1380	0.023*
C18	0.2893 (3)	−0.1876 (3)	0.05953 (17)	0.0223 (6)
H18	0.2036	−0.1666	0.0494	0.027*
C19	0.3379 (3)	−0.2884 (3)	0.02115 (17)	0.0222 (6)
H19	0.2869	−0.3362	−0.0157	0.027*
C20	0.4627 (3)	−0.3189 (2)	0.03732 (17)	0.0225 (6)
H20	0.4969	−0.3886	0.0113	0.027*
C21	0.5387 (3)	−0.2497 (2)	0.09078 (16)	0.0188 (5)
H21	0.6236	−0.2725	0.1018	0.023*

	U11	U22	U33	U12	U13	U23
Br1	0.0559 (2)	0.01873 (14)	0.02246 (14)	0.00349 (14)	−0.01182 (14)	0.00164 (12)
Br2	0.01697 (13)	0.03195 (17)	0.03461 (17)	0.00011 (12)	−0.00644 (13)	0.00337 (14)
N1	0.0142 (11)	0.0171 (11)	0.0151 (10)	−0.0003 (9)	−0.0004 (8)	0.0027 (10)
N2	0.0142 (11)	0.0189 (12)	0.0193 (10)	0.0029 (10)	−0.0035 (9)	−0.0018 (9)
C1	0.0191 (14)	0.0189 (13)	0.0172 (13)	0.0012 (12)	0.0014 (11)	−0.0035 (11)
C2	0.0227 (14)	0.0244 (16)	0.0208 (13)	0.0058 (13)	−0.0072 (12)	−0.0030 (13)
C3	0.0172 (14)	0.0140 (13)	0.0121 (12)	−0.0011 (10)	0.0006 (10)	0.0028 (10)
C4	0.0134 (13)	0.0182 (13)	0.0179 (13)	−0.0005 (10)	−0.0044 (11)	−0.0022 (11)
C5	0.0194 (14)	0.0231 (14)	0.0195 (14)	0.0009 (11)	−0.0028 (11)	−0.0035 (12)
C6	0.0255 (16)	0.0166 (14)	0.0269 (16)	0.0043 (12)	−0.0055 (13)	−0.0047 (12)
C7	0.0284 (17)	0.0171 (14)	0.0170 (13)	−0.0012 (12)	−0.0115 (12)	−0.0024 (12)
C8	0.0264 (17)	0.0217 (15)	0.0159 (13)	−0.0010 (12)	−0.0008 (12)	−0.0018 (11)
C9	0.0176 (14)	0.0183 (15)	0.0219 (13)	0.0058 (11)	−0.0012 (11)	−0.0030 (12)
C10	0.0150 (14)	0.0137 (13)	0.0136 (12)	−0.0018 (10)	0.0004 (10)	0.0022 (10)
C11	0.0209 (15)	0.0173 (14)	0.0156 (12)	−0.0048 (12)	−0.0016 (12)	−0.0017 (10)
C12	0.0203 (15)	0.0163 (14)	0.0232 (14)	0.0003 (11)	0.0030 (12)	0.0011 (11)
C13	0.0124 (13)	0.0239 (15)	0.0205 (13)	−0.0005 (11)	−0.0010 (11)	0.0094 (12)
C14	0.0222 (14)	0.0176 (13)	0.0173 (13)	−0.0044 (11)	−0.0033 (12)	0.0025 (11)
C15	0.0210 (14)	0.0143 (13)	0.0180 (13)	0.0003 (11)	0.0037 (11)	0.0002 (11)
C16	0.0189 (13)	0.0188 (12)	0.0126 (12)	−0.0049 (10)	0.0008 (11)	0.0013 (11)
C17	0.0218 (14)	0.0186 (13)	0.0181 (14)	−0.0005 (11)	−0.0008 (12)	0.0025 (12)
C18	0.0187 (15)	0.0292 (16)	0.0190 (14)	−0.0032 (13)	−0.0030 (13)	0.0058 (12)
C19	0.0255 (16)	0.0243 (16)	0.0168 (14)	−0.0098 (13)	−0.0023 (12)	0.0001 (12)
C20	0.0249 (16)	0.0230 (14)	0.0196 (14)	−0.0061 (13)	0.0040 (13)	−0.0033 (11)
C21	0.0159 (14)	0.0221 (13)	0.0183 (13)	−0.0028 (11)	0.0021 (12)	0.0021 (12)

Br1—C7	1.903 (3)	C9—H9	0.9500
Br2—C13	1.901 (2)	C10—C11	1.399 (4)
N1—C3	1.291 (3)	C10—C15	1.402 (4)
N1—N2	1.369 (3)	C11—C12	1.383 (4)
N2—C16	1.382 (3)	C11—H11	0.9500
N2—C1	1.478 (3)	C12—C13	1.385 (4)
C1—C4	1.512 (4)	C12—H12	0.9500
C1—C2	1.550 (4)	C13—C14	1.379 (4)
C1—H1	1.0000	C14—C15	1.377 (4)
C2—C3	1.506 (4)	C14—H14	0.9500
C2—H2A	0.9900	C15—H15	0.9500
C2—H2B	0.9900	C16—C17	1.397 (3)
C3—C10	1.461 (4)	C16—C21	1.407 (3)
C4—C9	1.390 (4)	C17—C18	1.383 (4)
C4—C5	1.391 (4)	C17—H17	0.9500
C5—C6	1.380 (4)	C18—C19	1.377 (4)
C5—H5	0.9500	C18—H18	0.9500
C6—C7	1.377 (4)	C19—C20	1.386 (4)
C6—H6	0.9500	C19—H19	0.9500
C7—C8	1.373 (4)	C20—C21	1.390 (4)
C8—C9	1.388 (4)	C20—H20	0.9500
C8—H8	0.9500	C21—H21	0.9500
C3—N1—N2	109.2 (2)	C11—C10—C15	118.4 (2)
N1—N2—C16	120.8 (2)	C11—C10—C3	121.0 (2)
N1—N2—C1	113.1 (2)	C15—C10—C3	120.6 (2)
C16—N2—C1	125.1 (2)	C12—C11—C10	120.6 (2)
N2—C1—C4	112.9 (2)	C12—C11—H11	119.7
N2—C1—C2	100.8 (2)	C10—C11—H11	119.7
C4—C1—C2	112.8 (2)	C11—C12—C13	119.3 (2)
N2—C1—H1	110.0	C11—C12—H12	120.3
C4—C1—H1	110.0	C13—C12—H12	120.3
C2—C1—H1	110.0	C14—C13—C12	121.3 (2)
C3—C2—C1	102.6 (2)	C14—C13—Br2	120.3 (2)
C3—C2—H2A	111.2	C12—C13—Br2	118.3 (2)
C1—C2—H2A	111.2	C15—C14—C13	119.2 (2)
C3—C2—H2B	111.2	C15—C14—H14	120.4
C1—C2—H2B	111.2	C13—C14—H14	120.4
H2A—C2—H2B	109.2	C14—C15—C10	121.1 (2)
N1—C3—C10	122.0 (2)	C14—C15—H15	119.4
N1—C3—C2	113.1 (2)	C10—C15—H15	119.4
C10—C3—C2	124.9 (2)	N2—C16—C17	120.9 (2)
C9—C4—C5	118.8 (2)	N2—C16—C21	120.3 (2)
C9—C4—C1	121.3 (2)	C17—C16—C21	118.8 (2)
C5—C4—C1	119.9 (2)	C18—C17—C16	120.3 (3)
C6—C5—C4	121.0 (2)	C18—C17—H17	119.9
C6—C5—H5	119.5	C16—C17—H17	119.9
C4—C5—H5	119.5	C19—C18—C17	121.4 (3)
C7—C6—C5	118.8 (2)	C19—C18—H18	119.3
C7—C6—H6	120.6	C17—C18—H18	119.3
C5—C6—H6	120.6	C18—C19—C20	118.7 (3)
C8—C7—C6	121.8 (2)	C18—C19—H19	120.6
C8—C7—Br1	118.3 (2)	C20—C19—H19	120.6
C6—C7—Br1	119.8 (2)	C19—C20—C21	121.4 (3)
C7—C8—C9	118.9 (2)	C19—C20—H20	119.3
C7—C8—H8	120.5	C21—C20—H20	119.3
C9—C8—H8	120.5	C20—C21—C16	119.5 (3)
C8—C9—C4	120.6 (2)	C20—C21—H21	120.3
C8—C9—H9	119.7	C16—C21—H21	120.3
C4—C9—H9	119.7
C3—N1—N2—C16	176.5 (2)	N1—C3—C10—C11	10.1 (4)
C3—N1—N2—C1	7.3 (3)	C2—C3—C10—C11	−171.9 (2)
N1—N2—C1—C4	110.1 (2)	N1—C3—C10—C15	−169.7 (2)
C16—N2—C1—C4	−58.6 (3)	C2—C3—C10—C15	8.4 (4)
N1—N2—C1—C2	−10.5 (3)	C15—C10—C11—C12	−0.1 (4)
C16—N2—C1—C2	−179.1 (2)	C3—C10—C11—C12	−179.8 (2)
N2—C1—C2—C3	9.2 (2)	C10—C11—C12—C13	0.6 (4)
C4—C1—C2—C3	−111.5 (2)	C11—C12—C13—C14	−0.4 (4)
N2—N1—C3—C10	178.0 (2)	C11—C12—C13—Br2	176.76 (19)
N2—N1—C3—C2	−0.3 (3)	C12—C13—C14—C15	−0.3 (4)
C1—C2—C3—N1	−6.1 (3)	Br2—C13—C14—C15	−177.42 (19)
C1—C2—C3—C10	175.7 (2)	C13—C14—C15—C10	0.8 (4)
N2—C1—C4—C9	−34.0 (3)	C11—C10—C15—C14	−0.7 (4)
C2—C1—C4—C9	79.5 (3)	C3—C10—C15—C14	179.1 (2)
N2—C1—C4—C5	148.6 (2)	N1—N2—C16—C17	178.2 (2)
C2—C1—C4—C5	−98.0 (3)	C1—N2—C16—C17	−13.9 (4)
C9—C4—C5—C6	−0.2 (4)	N1—N2—C16—C21	−1.9 (3)
C1—C4—C5—C6	177.3 (2)	C1—N2—C16—C21	165.9 (2)
C4—C5—C6—C7	0.4 (4)	N2—C16—C17—C18	179.0 (2)
C5—C6—C7—C8	0.2 (4)	C21—C16—C17—C18	−0.8 (4)
C5—C6—C7—Br1	179.2 (2)	C16—C17—C18—C19	−0.3 (4)
C6—C7—C8—C9	−1.1 (4)	C17—C18—C19—C20	0.9 (4)
Br1—C7—C8—C9	179.9 (2)	C18—C19—C20—C21	−0.3 (4)
C7—C8—C9—C4	1.3 (4)	C19—C20—C21—C16	−0.8 (4)
C5—C4—C9—C8	−0.6 (4)	N2—C16—C21—C20	−178.4 (2)
C1—C4—C9—C8	−178.1 (2)	C17—C16—C21—C20	1.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N1i	0.95	2.58	3.374 (3)	141
C20—H20···Br1ii	0.95	2.92	3.768 (2)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯N1i	0.95	2.58	3.374 (3)	141
C20—H20⋯Br1ii	0.95	2.92	3.768 (2)	148

Symmetry codes: (i) ; (ii) .