3-(4-Bromo­phen­yl)-5-(4-fluoro­phen­yl)-1-phenyl-4,5-dihydro-1H-pyrazole

In the title compound, C₂₁H₁₆BrFN₂, the pyrazoline ring forms dihedral angles of 8.1 (2), 14.2 (2) and 71.4 (2)° with the phenyl, 4-bromo­phenyl and 4-fluoro­phenyl substituents, respectively.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.043
• wR factor = 0.107
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large .......       1.10

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C7     = ...          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Pyrazolines are important five-membered heterocyclic compounds. 1-Acetyl-3,5-diaryl-2-pyrazolines have been found to inhibit the monoamine oxidases (Manna et al., 2002). 1,3,5-Triaryl-2-pyrazolines were also used as scintillation solutes (Wiley et al.,1958). Here we report the crystal strucutre of the title triaryl-2-pyrazoline. The title molecule is shown in Fig. 1; all bond lengths and bond angles are normal (Guo et al., 2006). The mean plane of pyrazoline ring N1/N2/C7—C9 is inclined to the best planes of the phenyl, 4-bromophenyl and 4-fluorophenyl substituents by 14.2 (2), 8.1 (2) and 71.4 (2)°, respectively.

Related literature

For information on arylpyrazolines, see: Manna et al. (2002); Wiley et al. (1958). For the crystal structure of a similar triarylpyrazoline derivative, see: Guo et al. (2006).

S2. Experimental

1-(4-Bromophenyl)-3-(4-fluorophenyl)-2-propenyl-1-ketone (0.02 mol) and phenylhydrazine (0.02 mol) were added to 99.5% acetic acid (40 ml) and stirred with refluxing for 6 h. The mixture was poured into ice-water to afford yellow solid. The solid was filtrated and washed with water until pH of the solution was about 7.0. Finally, the yellow solid was dried at room temperature. Single crystals of the title compound suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

S3. Refinement

H atoms were positioned geometrically and allowed to ride on their parent atoms with C—H distances of 0.93–0.96 Å and U_iso=1.2–1.5U_eq of the parent atoms.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The molecular structure with displacement ellipsoids drawn at the 30% probability level.

3-(4-Bromophenyl)-5-(4-fluorophenyl)-1-phenyl-4,5-dihydro-1H-pyrazole

Crystal data

C21H16BrFN2	F(000) = 800
Mr = 395.27	Dx = 1.501 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1936 reflections
a = 15.271 (3) Å	θ = 2.3–20.6°
b = 11.245 (2) Å	µ = 2.37 mm^−1
c = 10.727 (2) Å	T = 298 K
β = 108.321 (3)°	Plate, yellow
V = 1748.8 (6) Å^3	0.35 × 0.31 × 0.09 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer	3096 independent reflections
Radiation source: fine-focus sealed tube	1957 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
π and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −17→18
Tmin = 0.492, Tmax = 0.815	k = −13→11
7203 measured reflections	l = −12→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0175P)^2 + 1.2354P] where P = (Fo^2 + 2Fc^2)/3
3096 reflections	(Δ/σ)max = 0.001
226 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.63 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
C1	0.7173 (3)	0.3506 (4)	0.5661 (4)	0.0687 (10)
H1	0.7611	0.3543	0.6489	0.082*
C2	0.6527 (3)	0.4398 (4)	0.5276 (4)	0.0749 (11)
H2	0.6525	0.5035	0.5828	0.090*
C3	0.5896 (3)	0.4319 (4)	0.4071 (5)	0.0738 (11)
C4	0.5879 (3)	0.3412 (4)	0.3239 (4)	0.0792 (12)
H4	0.5437	0.3386	0.2413	0.095*
C5	0.6531 (3)	0.2524 (4)	0.3638 (4)	0.0740 (11)
H5	0.6524	0.1891	0.3078	0.089*
C6	0.7190 (2)	0.2564 (3)	0.4854 (3)	0.0598 (9)
C7	0.7940 (3)	0.1637 (3)	0.5307 (4)	0.0715 (10)
H7	0.8071	0.1486	0.6247	0.086*
C8	0.8841 (3)	0.1979 (4)	0.5025 (4)	0.0820 (12)
H8A	0.8796	0.2763	0.4635	0.098*
H8B	0.9366	0.1959	0.5821	0.098*
C9	0.8916 (3)	0.1039 (3)	0.4082 (3)	0.0633 (9)
C10	0.9613 (2)	0.0970 (3)	0.3421 (4)	0.0611 (9)
C11	1.0370 (3)	0.1734 (3)	0.3722 (4)	0.0723 (11)
H11	1.0435	0.2310	0.4367	0.087*
C12	1.1024 (3)	0.1657 (4)	0.3085 (4)	0.0762 (12)
H12	1.1523	0.2176	0.3298	0.091*
C13	1.0933 (2)	0.0813 (4)	0.2141 (4)	0.0723 (11)
C14	1.0200 (3)	0.0046 (4)	0.1822 (4)	0.0785 (11)
H14	1.0143	−0.0530	0.1178	0.094*
C15	0.9549 (3)	0.0129 (4)	0.2456 (4)	0.0753 (11)
H15	0.9051	−0.0393	0.2231	0.090*
C16	0.7075 (3)	−0.0327 (3)	0.4722 (4)	0.0658 (10)
C17	0.6978 (3)	−0.1413 (4)	0.4081 (4)	0.0710 (10)
H17	0.7320	−0.1576	0.3521	0.085*
C18	0.6379 (3)	−0.2246 (4)	0.4273 (4)	0.0801 (12)
H18	0.6315	−0.2969	0.3832	0.096*
C19	0.5869 (3)	−0.2037 (4)	0.5102 (4)	0.0831 (12)
H19	0.5475	−0.2617	0.5238	0.100*
C20	0.5951 (3)	−0.0962 (4)	0.5724 (4)	0.0834 (12)
H20	0.5604	−0.0808	0.6279	0.100*
C21	0.6544 (3)	−0.0102 (4)	0.5535 (4)	0.0770 (11)
H21	0.6588	0.0630	0.5954	0.092*
Br1	1.18176 (3)	0.06824 (5)	0.12420 (5)	0.0946 (2)
F1	0.52413 (17)	0.5188 (2)	0.3673 (3)	0.1060 (8)
N1	0.8282 (2)	0.0237 (3)	0.3876 (3)	0.0656 (8)
N2	0.7700 (2)	0.0519 (3)	0.4573 (3)	0.0780 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.077 (3)	0.068 (3)	0.062 (2)	−0.008 (2)	0.0222 (19)	−0.010 (2)
C2	0.085 (3)	0.062 (3)	0.087 (3)	−0.009 (2)	0.040 (3)	−0.015 (2)
C3	0.068 (3)	0.066 (3)	0.096 (3)	−0.001 (2)	0.040 (2)	0.010 (3)
C4	0.080 (3)	0.086 (3)	0.065 (3)	−0.011 (2)	0.015 (2)	0.010 (3)
C5	0.094 (3)	0.067 (3)	0.060 (3)	−0.009 (2)	0.024 (2)	−0.012 (2)
C6	0.073 (2)	0.053 (2)	0.059 (2)	−0.0068 (19)	0.0279 (19)	−0.0023 (19)
C7	0.088 (3)	0.060 (3)	0.068 (2)	−0.004 (2)	0.026 (2)	−0.004 (2)
C8	0.077 (3)	0.073 (3)	0.092 (3)	−0.004 (2)	0.021 (2)	−0.012 (2)
C9	0.066 (2)	0.055 (2)	0.063 (2)	0.0034 (19)	0.0113 (18)	0.0053 (19)
C10	0.053 (2)	0.052 (2)	0.069 (2)	0.0022 (17)	0.0070 (18)	0.0050 (19)
C11	0.061 (2)	0.061 (2)	0.083 (3)	−0.002 (2)	0.005 (2)	−0.004 (2)
C12	0.052 (2)	0.064 (3)	0.101 (3)	−0.0082 (19)	0.008 (2)	0.010 (2)
C13	0.054 (2)	0.066 (3)	0.091 (3)	0.0000 (19)	0.014 (2)	0.012 (2)
C14	0.071 (3)	0.066 (3)	0.103 (3)	−0.011 (2)	0.032 (2)	−0.010 (2)
C15	0.063 (2)	0.067 (3)	0.097 (3)	−0.018 (2)	0.026 (2)	−0.009 (2)
C16	0.067 (2)	0.058 (3)	0.071 (2)	0.0082 (19)	0.021 (2)	0.013 (2)
C17	0.068 (2)	0.061 (3)	0.088 (3)	0.002 (2)	0.029 (2)	−0.003 (2)
C18	0.075 (3)	0.062 (3)	0.106 (3)	−0.005 (2)	0.031 (2)	−0.004 (2)
C19	0.080 (3)	0.080 (3)	0.094 (3)	−0.008 (2)	0.033 (2)	0.012 (3)
C20	0.090 (3)	0.091 (4)	0.076 (3)	0.004 (3)	0.037 (2)	0.011 (3)
C21	0.095 (3)	0.067 (3)	0.075 (3)	0.003 (2)	0.036 (2)	0.001 (2)
Br1	0.0622 (3)	0.1061 (4)	0.1179 (4)	−0.0031 (2)	0.0318 (2)	0.0126 (3)
F1	0.0852 (17)	0.0916 (18)	0.148 (2)	0.0161 (15)	0.0462 (16)	0.0240 (17)
N1	0.072 (2)	0.0533 (19)	0.072 (2)	−0.0006 (16)	0.0236 (16)	0.0048 (16)
N2	0.092 (2)	0.053 (2)	0.102 (2)	−0.0041 (18)	0.050 (2)	−0.0085 (18)

Geometric parameters (Å, º)

C1—C6	1.374 (5)	C11—C12	1.378 (5)
C1—C2	1.376 (5)	C11—H11	0.9300
C1—H1	0.9300	C12—C13	1.363 (5)
C2—C3	1.351 (6)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.369 (5)
C3—C4	1.350 (6)	C13—Br1	1.897 (4)
C3—F1	1.367 (5)	C14—C15	1.374 (5)
C4—C5	1.379 (6)	C14—H14	0.9300
C4—H4	0.9300	C15—H15	0.9300
C5—C6	1.376 (5)	C16—C17	1.386 (5)
C5—H5	0.9300	C16—C21	1.388 (5)
C6—C7	1.511 (5)	C16—N2	1.392 (5)
C7—N2	1.468 (5)	C17—C18	1.370 (5)
C7—C8	1.547 (5)	C17—H17	0.9300
C7—H7	0.9800	C18—C19	1.374 (5)
C8—C9	1.492 (5)	C18—H18	0.9300
C8—H8A	0.9700	C19—C20	1.367 (6)
C8—H8B	0.9700	C19—H19	0.9300
C9—N1	1.290 (4)	C20—C21	1.383 (6)
C9—C10	1.456 (5)	C20—H20	0.9300
C10—C15	1.382 (5)	C21—H21	0.9300
C10—C11	1.394 (5)	N1—N2	1.367 (4)
C6—C1—C2	121.8 (4)	C12—C11—H11	119.2
C6—C1—H1	119.1	C10—C11—H11	119.2
C2—C1—H1	119.1	C13—C12—C11	119.5 (4)
C3—C2—C1	117.9 (4)	C13—C12—H12	120.3
C3—C2—H2	121.0	C11—C12—H12	120.3
C1—C2—H2	121.0	C12—C13—C14	120.6 (4)
C4—C3—C2	122.8 (4)	C12—C13—Br1	120.6 (3)
C4—C3—F1	118.3 (4)	C14—C13—Br1	118.8 (4)
C2—C3—F1	118.9 (4)	C13—C14—C15	119.7 (4)
C3—C4—C5	118.7 (4)	C13—C14—H14	120.2
C3—C4—H4	120.7	C15—C14—H14	120.2
C5—C4—H4	120.7	C14—C15—C10	121.7 (4)
C6—C5—C4	120.9 (4)	C14—C15—H15	119.2
C6—C5—H5	119.6	C10—C15—H15	119.2
C4—C5—H5	119.6	C17—C16—C21	118.7 (4)
C1—C6—C5	118.0 (4)	C17—C16—N2	121.0 (4)
C1—C6—C7	119.4 (3)	C21—C16—N2	120.3 (4)
C5—C6—C7	122.6 (3)	C18—C17—C16	120.0 (4)
N2—C7—C6	112.4 (3)	C18—C17—H17	120.0
N2—C7—C8	101.3 (3)	C16—C17—H17	120.0
C6—C7—C8	113.4 (3)	C17—C18—C19	121.4 (4)
N2—C7—H7	109.8	C17—C18—H18	119.3
C6—C7—H7	109.8	C19—C18—H18	119.3
C8—C7—H7	109.8	C20—C19—C18	118.9 (4)
C9—C8—C7	102.6 (3)	C20—C19—H19	120.5
C9—C8—H8A	111.2	C18—C19—H19	120.5
C7—C8—H8A	111.2	C19—C20—C21	120.7 (4)
C9—C8—H8B	111.2	C19—C20—H20	119.7
C7—C8—H8B	111.2	C21—C20—H20	119.7
H8A—C8—H8B	109.2	C20—C21—C16	120.2 (4)
N1—C9—C10	120.2 (4)	C20—C21—H21	119.9
N1—C9—C8	113.5 (3)	C16—C21—H21	119.9
C10—C9—C8	126.2 (3)	C9—N1—N2	109.0 (3)
C15—C10—C11	117.0 (4)	N1—N2—C16	119.4 (3)
C15—C10—C9	120.7 (3)	N1—N2—C7	113.4 (3)
C11—C10—C9	122.3 (4)	C16—N2—C7	126.1 (3)
C12—C11—C10	121.5 (4)
C6—C1—C2—C3	0.5 (6)	C11—C12—C13—Br1	179.9 (3)
C1—C2—C3—C4	−0.3 (6)	C12—C13—C14—C15	0.2 (6)
C1—C2—C3—F1	179.3 (3)	Br1—C13—C14—C15	−179.6 (3)
C2—C3—C4—C5	0.4 (6)	C13—C14—C15—C10	−0.3 (6)
F1—C3—C4—C5	−179.3 (3)	C11—C10—C15—C14	0.1 (6)
C3—C4—C5—C6	−0.6 (6)	C9—C10—C15—C14	−179.8 (4)
C2—C1—C6—C5	−0.7 (6)	C21—C16—C17—C18	−1.1 (6)
C2—C1—C6—C7	177.5 (3)	N2—C16—C17—C18	178.1 (4)
C4—C5—C6—C1	0.7 (6)	C16—C17—C18—C19	−0.5 (6)
C4—C5—C6—C7	−177.4 (4)	C17—C18—C19—C20	1.4 (6)
C1—C6—C7—N2	160.8 (3)	C18—C19—C20—C21	−0.7 (6)
C5—C6—C7—N2	−21.1 (5)	C19—C20—C21—C16	−0.8 (6)
C1—C6—C7—C8	−85.0 (4)	C17—C16—C21—C20	1.7 (6)
C5—C6—C7—C8	93.0 (4)	N2—C16—C21—C20	−177.4 (4)
N2—C7—C8—C9	4.5 (4)	C10—C9—N1—N2	−178.1 (3)
C6—C7—C8—C9	−116.2 (3)	C8—C9—N1—N2	1.9 (4)
C7—C8—C9—N1	−4.2 (4)	C9—N1—N2—C16	−167.0 (3)
C7—C8—C9—C10	175.8 (3)	C9—N1—N2—C7	1.5 (4)
N1—C9—C10—C15	7.4 (5)	C17—C16—N2—N1	−5.7 (5)
C8—C9—C10—C15	−172.7 (4)	C21—C16—N2—N1	173.4 (3)
N1—C9—C10—C11	−172.6 (3)	C17—C16—N2—C7	−172.7 (3)
C8—C9—C10—C11	7.4 (6)	C21—C16—N2—C7	6.5 (6)
C15—C10—C11—C12	0.1 (5)	C6—C7—N2—N1	117.4 (3)
C9—C10—C11—C12	−180.0 (3)	C8—C7—N2—N1	−3.9 (4)
C10—C11—C12—C13	−0.2 (6)	C6—C7—N2—C16	−75.0 (5)
C11—C12—C13—C14	0.0 (6)	C8—C7—N2—C16	163.7 (4)