3-(4-Chloro­phen­yl)-5-(4-fluoro­phen­yl)-1-phenyl-2-pyrazoline

In the title compound, C₂₁H₁₆ClFN₂, the pyrazoline ring forms dihedral angles of 14.88 (11)° with the phenyl ring, 74.59 (11)° with the fluoro­phenyl ring and 7.16 (10)° with the chloro­phenyl ring.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.039
• wR factor = 0.111
• Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found



Alert level A
DIFF020_ALERT_1_A  _diffrn_standards_interval_count and
            _diffrn_standards_interval_time are missing. Number of measurements
            between standards or time (min) between standards.
DIFF022_ALERT_1_A  _diffrn_standards_decay_% is missing
            Percentage decrease in standards intensity.

Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C15    = ...          R

   2 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

   4 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
   0 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

As important and useful five-membered heterocyclic compounds, pyrazoline and its derivatives were found to possess antiviral (Rawal et al., 1963), antifungal (Dhal et al., 1975), and immunosuppressive (Lombardino & Ottemes, 1981) activities. Several 1,3,5-triaryl-2-pyrazolines were also used as scintillation solutes (Wiley et al., 1958).

In the structure of the title compound (Fig. 1), all of the bond lengths and angles fall in the normal range (Rurack et al., 2000; Fahrni et al., 2003; Guo, et al., 2006; Foces-Foces et al., 2001). The mean planes of the pyrazolinyl ring N1/N2/C7/C14/C15 and benzene ring C1—C6 and benzene ring C16—C21 and benzene ring C8—C13 make dihedral angles of 14.88 (11)°, 74.59 (11)° and 7.16 (10)°, respectively.

Related literature

For related literature, see: Dhal et al. (1975); Fahrni et al. (2003); Foces-Foces, Jagerovic & Elguero (2001); Guo et al. (2006); Lombardino & Ottemes (1981); Rawal et al. (1963); Rurack et al. (2000); Wiley et al. (1958).

S2. Experimental

1-(p-Chlorophenyl)-3-(p-fluorophenyl)-2-propenyl-1-ketone (0.02 mol) and phenylhydrazine (0.02 mol) were mixed in 99.5% acetic acid (40 ml) and stirred in at reflux for 6 h. Then the mixture was poured into ice-water to afford yellow solids. The solids were filtered and washed with water until the pH of solution was about 7.0. Finally, the red solid crystals were dried at room temperature. Single crystals of the title compound suitable for X-ray measurements were obtained by recrystallization from EtOH at room temperature.

S3. Refinement

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

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); 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 and atom-labeling scheme with displacement ellipsoids drawn at the 30% probability level.

3-(4-Chlorophenyl)-5-(4-fluorophenyl)-1-phenyl-2-pyrazoline

Crystal data

C21H16ClFN2	F(000) = 728
Mr = 350.81	Dx = 1.351 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3206 reflections
a = 14.675 (3) Å	θ = 2.3–25.0°
b = 11.271 (2) Å	µ = 0.24 mm^−1
c = 11.086 (2) Å	T = 298 K
β = 109.818 (2)°	Plate, yellow
V = 1725.0 (5) Å^3	0.48 × 0.47 × 0.23 mm
Z = 4

Data collection

Bruker SMART 1000 diffractometer	2319 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Graphite monochromator	θmax = 25.0°, θmin = 2.3°
φ and ω scans	h = −17→14
7111 measured reflections	k = −13→11
3044 independent reflections	l = −13→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.111	w = 1/[σ^2(Fo^2) + (0.0508P)^2 + 0.3475P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3044 reflections	Δρmax = 0.22 e Å^−3
227 parameters	Δρmin = −0.26 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0162 (16)

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	0.16149 (15)	1.01229 (18)	0.5524 (2)	0.0695 (5)
H1	0.1676	0.9390	0.5928	0.083*
C2	0.10157 (15)	1.0974 (2)	0.5741 (2)	0.0761 (6)
H2	0.0678	1.0812	0.6297	0.091*
C3	0.09107 (16)	1.2057 (2)	0.5150 (2)	0.0802 (6)
H3	0.0513	1.2634	0.5309	0.096*
C4	0.14050 (15)	1.2278 (2)	0.4311 (2)	0.0764 (6)
H4	0.1330	1.3007	0.3894	0.092*
C5	0.20035 (13)	1.14404 (17)	0.4084 (2)	0.0657 (5)
H5	0.2327	1.1600	0.3511	0.079*
C6	0.21268 (13)	1.03529 (16)	0.47079 (18)	0.0589 (5)
C7	0.40002 (13)	0.89975 (15)	0.39970 (17)	0.0555 (4)
C8	0.46938 (12)	0.90608 (15)	0.33153 (17)	0.0536 (4)
C9	0.45956 (14)	0.99101 (18)	0.2369 (2)	0.0647 (5)
H9	0.4078	1.0438	0.2166	0.078*
C10	0.52438 (15)	0.99847 (18)	0.1732 (2)	0.0672 (5)
H10	0.5169	1.0563	0.1107	0.081*
C11	0.60067 (13)	0.92043 (17)	0.20149 (19)	0.0615 (5)
C12	0.61265 (13)	0.83497 (18)	0.2935 (2)	0.0660 (5)
H12	0.6643	0.7821	0.3122	0.079*
C13	0.54739 (13)	0.82807 (16)	0.35827 (19)	0.0619 (5)
H13	0.5556	0.7703	0.4209	0.074*
C14	0.39643 (14)	0.80659 (18)	0.4945 (2)	0.0707 (6)
H14A	0.4533	0.8101	0.5713	0.085*
H14B	0.3913	0.7278	0.4577	0.085*
C15	0.30424 (14)	0.83989 (17)	0.52346 (19)	0.0645 (5)
H15	0.3206	0.8545	0.6155	0.077*
C16	0.22526 (13)	0.74734 (16)	0.48031 (17)	0.0543 (4)
C17	0.15803 (16)	0.74724 (19)	0.35858 (19)	0.0694 (5)
H17	0.1586	0.8079	0.3020	0.083*
C18	0.08956 (15)	0.6581 (2)	0.3194 (2)	0.0772 (6)
H18	0.0443	0.6582	0.2369	0.093*
C19	0.08968 (15)	0.57080 (18)	0.4032 (2)	0.0705 (6)
C20	0.15420 (16)	0.56749 (18)	0.5242 (2)	0.0722 (6)
H20	0.1526	0.5066	0.5801	0.087*
C21	0.22215 (14)	0.65665 (17)	0.56219 (19)	0.0629 (5)
H21	0.2669	0.6556	0.6450	0.076*
Cl1	0.68197 (4)	0.93159 (6)	0.11870 (6)	0.0864 (2)
F1	0.02159 (10)	0.48410 (12)	0.36443 (17)	0.1071 (5)
N1	0.33374 (11)	0.97931 (13)	0.38178 (15)	0.0591 (4)
N2	0.27689 (12)	0.95195 (14)	0.45308 (18)	0.0706 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0769 (13)	0.0621 (12)	0.0773 (14)	−0.0086 (10)	0.0365 (11)	−0.0067 (10)
C2	0.0720 (13)	0.0861 (16)	0.0797 (15)	−0.0070 (11)	0.0383 (12)	−0.0169 (12)
C3	0.0695 (13)	0.0755 (15)	0.1011 (17)	0.0093 (11)	0.0359 (13)	−0.0130 (13)
C4	0.0676 (13)	0.0669 (13)	0.0992 (17)	0.0087 (10)	0.0342 (12)	0.0036 (11)
C5	0.0599 (11)	0.0627 (12)	0.0792 (14)	−0.0012 (9)	0.0298 (10)	−0.0011 (10)
C6	0.0572 (10)	0.0545 (11)	0.0680 (12)	−0.0062 (8)	0.0249 (9)	−0.0094 (9)
C7	0.0544 (10)	0.0519 (10)	0.0564 (11)	−0.0036 (8)	0.0138 (8)	−0.0067 (8)
C8	0.0488 (9)	0.0511 (10)	0.0563 (10)	−0.0045 (8)	0.0117 (8)	−0.0077 (8)
C9	0.0606 (11)	0.0622 (12)	0.0727 (13)	0.0122 (9)	0.0244 (10)	0.0037 (10)
C10	0.0691 (12)	0.0646 (12)	0.0726 (13)	0.0062 (10)	0.0301 (10)	0.0064 (10)
C11	0.0521 (10)	0.0639 (12)	0.0673 (12)	−0.0030 (9)	0.0186 (9)	−0.0095 (10)
C12	0.0476 (10)	0.0629 (12)	0.0828 (14)	0.0039 (9)	0.0162 (10)	−0.0053 (10)
C13	0.0543 (10)	0.0564 (11)	0.0702 (12)	0.0003 (9)	0.0149 (9)	0.0018 (9)
C14	0.0655 (12)	0.0653 (12)	0.0826 (14)	0.0041 (10)	0.0267 (11)	0.0095 (10)
C15	0.0737 (12)	0.0590 (11)	0.0644 (12)	−0.0008 (10)	0.0281 (10)	0.0020 (9)
C16	0.0621 (11)	0.0526 (10)	0.0534 (11)	0.0058 (8)	0.0261 (9)	0.0030 (8)
C17	0.0821 (13)	0.0694 (12)	0.0580 (12)	0.0037 (11)	0.0253 (11)	0.0081 (10)
C18	0.0697 (13)	0.0881 (16)	0.0673 (13)	0.0072 (12)	0.0146 (11)	−0.0094 (12)
C19	0.0580 (11)	0.0613 (12)	0.1002 (17)	−0.0005 (10)	0.0375 (12)	−0.0121 (12)
C20	0.0762 (13)	0.0593 (12)	0.0931 (17)	0.0044 (11)	0.0444 (13)	0.0142 (11)
C21	0.0656 (11)	0.0675 (12)	0.0584 (11)	0.0066 (10)	0.0245 (9)	0.0102 (9)
Cl1	0.0664 (3)	0.1100 (5)	0.0926 (4)	0.0053 (3)	0.0396 (3)	−0.0006 (3)
F1	0.0793 (8)	0.0874 (9)	0.1598 (14)	−0.0181 (7)	0.0471 (9)	−0.0274 (9)
N1	0.0639 (9)	0.0518 (9)	0.0673 (10)	−0.0021 (7)	0.0295 (8)	−0.0041 (7)
N2	0.0801 (11)	0.0528 (9)	0.0963 (13)	0.0052 (8)	0.0525 (10)	0.0086 (8)

Geometric parameters (Å, º)

C1—C2	1.377 (3)	C11—Cl1	1.739 (2)
C1—C6	1.382 (3)	C12—C13	1.380 (3)
C1—H1	0.9300	C12—H12	0.9300
C2—C3	1.370 (3)	C13—H13	0.9300
C2—H2	0.9300	C14—C15	1.539 (3)
C3—C4	1.382 (3)	C14—H14A	0.9700
C3—H3	0.9300	C14—H14B	0.9700
C4—C5	1.370 (3)	C15—N2	1.467 (2)
C4—H4	0.9300	C15—C16	1.511 (3)
C5—C6	1.389 (3)	C15—H15	0.9800
C5—H5	0.9300	C16—C17	1.375 (3)
C6—N2	1.391 (2)	C16—C21	1.378 (3)
C7—N1	1.288 (2)	C17—C18	1.382 (3)
C7—C8	1.461 (3)	C17—H17	0.9300
C7—C14	1.499 (3)	C18—C19	1.353 (3)
C8—C9	1.391 (3)	C18—H18	0.9300
C8—C13	1.393 (2)	C19—C20	1.355 (3)
C9—C10	1.366 (3)	C19—F1	1.359 (2)
C9—H9	0.9300	C20—C21	1.377 (3)
C10—C11	1.374 (3)	C20—H20	0.9300
C10—H10	0.9300	C21—H21	0.9300
C11—C12	1.370 (3)	N1—N2	1.365 (2)
C2—C1—C6	120.3 (2)	C12—C13—H13	119.4
C2—C1—H1	119.8	C8—C13—H13	119.4
C6—C1—H1	119.8	C7—C14—C15	102.57 (15)
C3—C2—C1	120.8 (2)	C7—C14—H14A	111.3
C3—C2—H2	119.6	C15—C14—H14A	111.3
C1—C2—H2	119.6	C7—C14—H14B	111.3
C2—C3—C4	118.9 (2)	C15—C14—H14B	111.3
C2—C3—H3	120.5	H14A—C14—H14B	109.2
C4—C3—H3	120.5	N2—C15—C16	112.56 (16)
C5—C4—C3	121.0 (2)	N2—C15—C14	101.57 (15)
C5—C4—H4	119.5	C16—C15—C14	113.56 (16)
C3—C4—H4	119.5	N2—C15—H15	109.6
C4—C5—C6	120.00 (19)	C16—C15—H15	109.6
C4—C5—H5	120.0	C14—C15—H15	109.6
C6—C5—H5	120.0	C17—C16—C21	118.21 (18)
C1—C6—C5	118.92 (18)	C17—C16—C15	121.95 (17)
C1—C6—N2	120.68 (18)	C21—C16—C15	119.77 (17)
C5—C6—N2	120.38 (17)	C16—C17—C18	120.82 (19)
N1—C7—C8	120.56 (17)	C16—C17—H17	119.6
N1—C7—C14	113.05 (16)	C18—C17—H17	119.6
C8—C7—C14	126.39 (16)	C19—C18—C17	118.7 (2)
C9—C8—C13	117.54 (17)	C19—C18—H18	120.6
C9—C8—C7	120.77 (16)	C17—C18—H18	120.6
C13—C8—C7	121.69 (17)	C18—C19—C20	122.5 (2)
C10—C9—C8	121.34 (18)	C18—C19—F1	118.4 (2)
C10—C9—H9	119.3	C20—C19—F1	119.0 (2)
C8—C9—H9	119.3	C19—C20—C21	118.23 (19)
C9—C10—C11	119.90 (19)	C19—C20—H20	120.9
C9—C10—H10	120.0	C21—C20—H20	120.9
C11—C10—H10	120.0	C20—C21—C16	121.48 (19)
C12—C11—C10	120.61 (18)	C20—C21—H21	119.3
C12—C11—Cl1	120.39 (15)	C16—C21—H21	119.3
C10—C11—Cl1	118.99 (16)	C7—N1—N2	109.35 (15)
C11—C12—C13	119.36 (18)	N1—N2—C6	120.37 (15)
C11—C12—H12	120.3	N1—N2—C15	113.06 (14)
C13—C12—H12	120.3	C6—N2—C15	125.63 (16)
C12—C13—C8	121.25 (18)
C6—C1—C2—C3	0.4 (3)	N2—C15—C16—C17	26.7 (2)
C1—C2—C3—C4	1.0 (3)	C14—C15—C16—C17	−88.0 (2)
C2—C3—C4—C5	−1.0 (3)	N2—C15—C16—C21	−156.32 (16)
C3—C4—C5—C6	−0.5 (3)	C14—C15—C16—C21	89.0 (2)
C2—C1—C6—C5	−1.9 (3)	C21—C16—C17—C18	−0.4 (3)
C2—C1—C6—N2	176.89 (19)	C15—C16—C17—C18	176.66 (18)
C4—C5—C6—C1	2.0 (3)	C16—C17—C18—C19	0.1 (3)
C4—C5—C6—N2	−176.86 (19)	C17—C18—C19—C20	0.2 (3)
N1—C7—C8—C9	−6.4 (3)	C17—C18—C19—F1	179.38 (17)
C14—C7—C8—C9	174.00 (18)	C18—C19—C20—C21	−0.2 (3)
N1—C7—C8—C13	173.63 (16)	F1—C19—C20—C21	−179.45 (16)
C14—C7—C8—C13	−6.0 (3)	C19—C20—C21—C16	0.0 (3)
C13—C8—C9—C10	−0.5 (3)	C17—C16—C21—C20	0.3 (3)
C7—C8—C9—C10	179.47 (17)	C15—C16—C21—C20	−176.80 (17)
C8—C9—C10—C11	0.5 (3)	C8—C7—N1—N2	178.28 (15)
C9—C10—C11—C12	−0.1 (3)	C14—C7—N1—N2	−2.0 (2)
C9—C10—C11—Cl1	179.85 (16)	C7—N1—N2—C6	167.07 (17)
C10—C11—C12—C13	−0.2 (3)	C7—N1—N2—C15	−2.5 (2)
Cl1—C11—C12—C13	179.79 (15)	C1—C6—N2—N1	−173.95 (17)
C11—C12—C13—C8	0.2 (3)	C5—C6—N2—N1	4.9 (3)
C9—C8—C13—C12	0.2 (3)	C1—C6—N2—C15	−5.8 (3)
C7—C8—C13—C12	−179.84 (17)	C5—C6—N2—C15	173.00 (18)
N1—C7—C14—C15	5.3 (2)	C16—C15—N2—N1	−116.27 (17)
C8—C7—C14—C15	−175.02 (16)	C14—C15—N2—N1	5.5 (2)
C7—C14—C15—N2	−5.97 (19)	C16—C15—N2—C6	74.8 (2)
C7—C14—C15—C16	115.13 (18)	C14—C15—N2—C6	−163.37 (19)