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

The title compound, C₂₂H₁₉ClN₂, was prepared by the reaction of phenyl­hydrazine and 1-(4-chloro­phen­yl)-3-(4-methyl­phen­yl)prop-2-en-1-one. The pyrazoline ring forms dihedral angles of 1.50 (5)° with the phenyl ring, 8.44 (2)° with the chloro­phenyl ring and 80.07 (1)° with the tolyl ring.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.055
• wR factor = 0.145
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C13
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.47
           From the CIF: _reflns_number_total               3715
           Count of symmetry unique reflns         2170
           Completeness (_total/calc)            171.20%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1545
           Fraction of Friedel pairs measured     0.712
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C9     = .          S

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Pyrazoline and its derivatives are important and useful five-membered heterocyclic compounds, which are found to possess antiviral (Rawal et al., 1963), antifungal (Dhal et al., 1975), and immunosuppressive (Lombardino & Ottemes, 1981) activities. 1-Acetyl-3,5-diaryl-2-pyrazoline have been found to inhibit monoamine oxidases (Manna et al., 2002). As part of our ongoing investgation of pyrazolines and their metal complexes, we report here the crystal structure of the title compound. In the structure of the title compound, all bond lengthes and bond angles fall in the normal range (Rurack et al., 2000; Fahrni et al., 2003; Ge, 2006; Guo et al., 2006; Kimura et al., 1977). The pyrazoline ring forms dihedral angles of 1.50 (5)° with the phenyl ring, 8.44 (2)° with the chlorophenyl ring and 80.07 (1)° with the tolyl ring.

Related literature

For related literature, see: Dhal et al. (1975); Fahrni et al. (2003); Ge (2006); Guo et al. (2006); Kimura et al. (1977); Lombardino & Ottemes (1981); Rawal et al. (1963); Rurack et al. (2000); Manna et al. (2002).

S2. Experimental

1-(4-chlorophenyl)-3-(4-methylphenyl)-2-propenyl-1-ketone (0.02 mol) and phenylhydrazine (0.02 mol) were mixed in acetic acid (40 ml) and stirred under reflux for 6 h. Then, the mixture was poured into ice-water to afford a light yellow solid which was filtrated and washed with water until the pH of the solution was about 7.0. Finally, the yellow solid was dry 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 geometrically positioned and allowed to ride on their parent atoms with C—H distances ranging from 0.93 to 0.96 Å, and with U_iso=1.2U_eq(C) or U_iso=1.5U_eq(C_methyl). The methyl group was allowed to rotate but not to tip.

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 for (I), with displacement ellipsoids drawn at the 30% probability level.

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

Crystal data

C22H19ClN2	F(000) = 728
Mr = 346.84	Dx = 1.211 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 1354 reflections
a = 23.614 (11) Å	θ = 2.4–20.7°
b = 5.698 (3) Å	µ = 0.21 mm^−1
c = 14.232 (6) Å	T = 294 K
β = 96.557 (8)°	Block, yellow
V = 1902.6 (15) Å^3	0.36 × 0.20 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	3715 independent reflections
Radiation source: fine-focus sealed tube	2190 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
φ and ω scans	θmax = 26.5°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −29→14
Tmin = 0.929, Tmax = 0.960	k = −7→7
5424 measured reflections	l = −14→17

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)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.145	w = 1/[σ^2(Fo^2) + (0.0683P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.001
3715 reflections	Δρmax = 0.16 e Å^−3
227 parameters	Δρmin = −0.22 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1575 Friedel Pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (10)

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
Cl1	0.73839 (4)	−0.3110 (2)	−0.21682 (6)	0.0832 (4)
N1	0.57116 (11)	−0.0088 (5)	0.12353 (18)	0.0557 (7)
N2	0.54873 (12)	−0.0243 (6)	0.2088 (2)	0.0673 (9)
C1	0.63565 (14)	−0.0426 (6)	−0.0378 (2)	0.0546 (9)
H1	0.6129	0.0899	−0.0347	0.066*
C2	0.66528 (15)	−0.0759 (7)	−0.1148 (2)	0.0584 (9)
H2	0.6622	0.0336	−0.1636	0.070*
C3	0.69960 (13)	−0.2719 (7)	−0.1199 (2)	0.0542 (9)
C4	0.70369 (13)	−0.4384 (6)	−0.0491 (2)	0.0549 (9)
H4	0.7262	−0.5709	−0.0534	0.066*
C5	0.67375 (13)	−0.4067 (6)	0.0290 (2)	0.0526 (8)
H5	0.6766	−0.5190	0.0768	0.063*
C6	0.63962 (13)	−0.2088 (6)	0.0365 (2)	0.0461 (8)
C7	0.60807 (13)	−0.1782 (6)	0.1194 (2)	0.0497 (8)
C8	0.61383 (13)	−0.3355 (7)	0.2059 (2)	0.0596 (9)
H8A	0.6533	−0.3478	0.2334	0.071*
H8B	0.5991	−0.4915	0.1906	0.071*
C9	0.57695 (13)	−0.2056 (7)	0.2740 (2)	0.0581 (9)
H9	0.5483	−0.3128	0.2943	0.070*
C10	0.61184 (14)	−0.0972 (6)	0.3604 (2)	0.0527 (9)
C11	0.61394 (16)	−0.1990 (7)	0.4492 (3)	0.0687 (10)
H11	0.5935	−0.3359	0.4568	0.082*
C12	0.64627 (17)	−0.0988 (8)	0.5272 (3)	0.0758 (12)
H12	0.6469	−0.1711	0.5859	0.091*
C13	0.67719 (14)	0.1039 (7)	0.5199 (3)	0.0641 (10)
C14	0.67548 (15)	0.2027 (8)	0.4303 (3)	0.0713 (10)
H14	0.6964	0.3383	0.4225	0.086*
C15	0.64357 (14)	0.1053 (7)	0.3523 (3)	0.0634 (10)
H15	0.6434	0.1768	0.2935	0.076*
C16	0.71137 (17)	0.2189 (10)	0.6050 (3)	0.0929 (13)
H16A	0.7087	0.1247	0.6603	0.139*
H16B	0.6963	0.3724	0.6146	0.139*
H16C	0.7506	0.2318	0.5938	0.139*
C17	0.50758 (12)	0.1382 (7)	0.2305 (2)	0.0576 (9)
C18	0.48671 (14)	0.1344 (9)	0.3186 (3)	0.0790 (12)
H18	0.4996	0.0222	0.3635	0.095*
C19	0.44610 (16)	0.3015 (10)	0.3387 (3)	0.0926 (15)
H19	0.4323	0.2994	0.3973	0.111*
C20	0.42645 (17)	0.4677 (9)	0.2732 (4)	0.0899 (14)
H20	0.3998	0.5783	0.2879	0.108*
C21	0.44620 (16)	0.4709 (9)	0.1856 (3)	0.0837 (13)
H21	0.4325	0.5828	0.1411	0.100*
C22	0.48642 (14)	0.3075 (8)	0.1636 (3)	0.0677 (10)
H22	0.4994	0.3103	0.1043	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0870 (6)	0.1050 (9)	0.0608 (6)	−0.0051 (7)	0.0219 (5)	−0.0197 (6)
N1	0.0523 (16)	0.0607 (19)	0.0538 (17)	0.0134 (15)	0.0050 (14)	0.0023 (15)
N2	0.0647 (18)	0.081 (2)	0.0590 (18)	0.0284 (18)	0.0186 (15)	0.0098 (18)
C1	0.062 (2)	0.047 (2)	0.055 (2)	0.0068 (18)	0.0068 (17)	0.0026 (18)
C2	0.073 (2)	0.052 (2)	0.049 (2)	−0.006 (2)	0.0048 (18)	0.0021 (18)
C3	0.0514 (18)	0.065 (2)	0.0471 (18)	−0.0036 (19)	0.0083 (15)	−0.0104 (19)
C4	0.0518 (19)	0.052 (2)	0.060 (2)	0.0076 (16)	0.0026 (17)	−0.0105 (19)
C5	0.0538 (17)	0.048 (2)	0.055 (2)	0.0078 (17)	0.0040 (16)	0.0055 (17)
C6	0.0452 (16)	0.0459 (19)	0.0458 (18)	0.0002 (16)	−0.0005 (14)	0.0012 (15)
C7	0.0474 (17)	0.050 (2)	0.0506 (19)	0.0046 (17)	0.0007 (15)	−0.0014 (17)
C8	0.0660 (19)	0.058 (2)	0.0562 (19)	0.009 (2)	0.0112 (16)	0.0097 (19)
C9	0.0570 (19)	0.058 (2)	0.061 (2)	0.0067 (18)	0.0129 (17)	0.010 (2)
C10	0.0565 (19)	0.050 (2)	0.055 (2)	0.0079 (16)	0.0212 (17)	0.0109 (17)
C11	0.092 (3)	0.055 (2)	0.063 (2)	−0.016 (2)	0.023 (2)	0.008 (2)
C12	0.104 (3)	0.073 (3)	0.052 (2)	−0.008 (3)	0.015 (2)	0.005 (2)
C13	0.066 (2)	0.060 (3)	0.069 (3)	0.001 (2)	0.0210 (19)	−0.005 (2)
C14	0.067 (2)	0.058 (2)	0.092 (3)	−0.003 (2)	0.021 (2)	0.012 (3)
C15	0.065 (2)	0.060 (2)	0.067 (2)	−0.006 (2)	0.0146 (19)	0.020 (2)
C16	0.100 (3)	0.091 (3)	0.086 (3)	−0.002 (3)	0.007 (2)	−0.017 (3)
C17	0.0423 (16)	0.065 (2)	0.065 (2)	0.0058 (18)	0.0028 (16)	−0.007 (2)
C18	0.062 (2)	0.099 (3)	0.080 (3)	0.011 (2)	0.026 (2)	−0.002 (3)
C19	0.062 (2)	0.126 (4)	0.095 (3)	0.010 (3)	0.031 (2)	−0.019 (3)
C20	0.062 (2)	0.096 (4)	0.113 (4)	0.025 (3)	0.011 (3)	−0.021 (3)
C21	0.066 (2)	0.090 (3)	0.093 (3)	0.025 (2)	0.000 (2)	−0.016 (3)
C22	0.0519 (19)	0.081 (3)	0.067 (2)	0.011 (2)	−0.0046 (18)	−0.013 (2)

Geometric parameters (Å, º)

Cl1—C3	1.755 (3)	C11—C12	1.396 (5)
N1—C7	1.306 (4)	C11—H11	0.9300
N1—N2	1.382 (4)	C12—C13	1.377 (5)
N2—C17	1.402 (4)	C12—H12	0.9300
N2—C9	1.493 (4)	C13—C14	1.390 (5)
C1—C2	1.379 (4)	C13—C16	1.525 (5)
C1—C6	1.415 (4)	C14—C15	1.384 (5)
C1—H1	0.9300	C14—H14	0.9300
C2—C3	1.387 (5)	C15—H15	0.9300
C2—H2	0.9300	C16—H16A	0.9600
C3—C4	1.379 (5)	C16—H16B	0.9600
C4—C5	1.396 (4)	C16—H16C	0.9600
C4—H4	0.9300	C17—C18	1.399 (5)
C5—C6	1.398 (4)	C17—C22	1.407 (5)
C5—H5	0.9300	C18—C19	1.404 (6)
C6—C7	1.476 (4)	C18—H18	0.9300
C7—C8	1.517 (4)	C19—C20	1.372 (7)
C8—C9	1.561 (4)	C19—H19	0.9300
C8—H8A	0.9700	C20—C21	1.380 (6)
C8—H8B	0.9700	C20—H20	0.9300
C9—C10	1.530 (5)	C21—C22	1.391 (5)
C9—H9	0.9800	C21—H21	0.9300
C10—C11	1.386 (5)	C22—H22	0.9300
C10—C15	1.388 (5)
C7—N1—N2	108.5 (3)	C10—C11—C12	120.9 (3)
N1—N2—C17	119.7 (3)	C10—C11—H11	119.5
N1—N2—C9	113.6 (2)	C12—C11—H11	119.5
C17—N2—C9	126.3 (3)	C13—C12—C11	121.9 (4)
C2—C1—C6	120.4 (3)	C13—C12—H12	119.0
C2—C1—H1	119.8	C11—C12—H12	119.0
C6—C1—H1	119.8	C12—C13—C14	116.7 (4)
C1—C2—C3	120.3 (3)	C12—C13—C16	122.5 (4)
C1—C2—H2	119.8	C14—C13—C16	120.8 (4)
C3—C2—H2	119.8	C15—C14—C13	121.9 (4)
C4—C3—C2	120.6 (3)	C15—C14—H14	119.0
C4—C3—Cl1	119.2 (3)	C13—C14—H14	119.0
C2—C3—Cl1	120.2 (3)	C14—C15—C10	121.1 (3)
C3—C4—C5	119.5 (3)	C14—C15—H15	119.4
C3—C4—H4	120.2	C10—C15—H15	119.4
C5—C4—H4	120.2	C13—C16—H16A	109.5
C4—C5—C6	120.9 (3)	C13—C16—H16B	109.5
C4—C5—H5	119.5	H16A—C16—H16B	109.5
C6—C5—H5	119.5	C13—C16—H16C	109.5
C5—C6—C1	118.2 (3)	H16A—C16—H16C	109.5
C5—C6—C7	120.3 (3)	H16B—C16—H16C	109.5
C1—C6—C7	121.5 (3)	C18—C17—N2	120.7 (3)
N1—C7—C6	121.5 (3)	C18—C17—C22	118.9 (3)
N1—C7—C8	113.5 (3)	N2—C17—C22	120.4 (3)
C6—C7—C8	124.9 (3)	C17—C18—C19	119.4 (4)
C7—C8—C9	102.6 (3)	C17—C18—H18	120.3
C7—C8—H8A	111.2	C19—C18—H18	120.3
C9—C8—H8A	111.2	C20—C19—C18	121.1 (4)
C7—C8—H8B	111.2	C20—C19—H19	119.4
C9—C8—H8B	111.2	C18—C19—H19	119.4
H8A—C8—H8B	109.2	C19—C20—C21	120.0 (4)
N2—C9—C10	112.4 (3)	C19—C20—H20	120.0
N2—C9—C8	100.6 (2)	C21—C20—H20	120.0
C10—C9—C8	113.7 (3)	C20—C21—C22	120.3 (4)
N2—C9—H9	109.9	C20—C21—H21	119.8
C10—C9—H9	109.9	C22—C21—H21	119.8
C8—C9—H9	109.9	C21—C22—C17	120.3 (4)
C11—C10—C15	117.4 (4)	C21—C22—H22	119.8
C11—C10—C9	121.6 (3)	C17—C22—H22	119.8
C15—C10—C9	121.0 (3)
C7—N1—N2—C17	−179.7 (3)	N2—C9—C10—C11	142.3 (3)
C7—N1—N2—C9	6.6 (4)	C8—C9—C10—C11	−104.2 (4)
C6—C1—C2—C3	−0.4 (5)	N2—C9—C10—C15	−39.0 (4)
C1—C2—C3—C4	1.3 (5)	C8—C9—C10—C15	74.5 (4)
C1—C2—C3—Cl1	−178.7 (3)	C15—C10—C11—C12	0.8 (5)
C2—C3—C4—C5	−1.1 (5)	C9—C10—C11—C12	179.6 (3)
Cl1—C3—C4—C5	178.9 (2)	C10—C11—C12—C13	0.1 (6)
C3—C4—C5—C6	0.1 (5)	C11—C12—C13—C14	−1.0 (6)
C4—C5—C6—C1	0.8 (4)	C11—C12—C13—C16	178.3 (4)
C4—C5—C6—C7	179.8 (3)	C12—C13—C14—C15	1.1 (6)
C2—C1—C6—C5	−0.6 (4)	C16—C13—C14—C15	−178.2 (3)
C2—C1—C6—C7	−179.6 (3)	C13—C14—C15—C10	−0.2 (6)
N2—N1—C7—C6	−179.9 (3)	C11—C10—C15—C14	−0.7 (5)
N2—N1—C7—C8	0.9 (4)	C9—C10—C15—C14	−179.6 (3)
C5—C6—C7—N1	−172.5 (3)	N1—N2—C17—C18	−176.2 (3)
C1—C6—C7—N1	6.5 (5)	C9—N2—C17—C18	−3.3 (5)
C5—C6—C7—C8	6.7 (5)	N1—N2—C17—C22	4.0 (5)
C1—C6—C7—C8	−174.3 (3)	C9—N2—C17—C22	176.9 (3)
N1—C7—C8—C9	−7.2 (4)	N2—C17—C18—C19	179.1 (4)
C6—C7—C8—C9	173.6 (3)	C22—C17—C18—C19	−1.1 (5)
N1—N2—C9—C10	110.9 (3)	C17—C18—C19—C20	0.2 (6)
C17—N2—C9—C10	−62.4 (4)	C18—C19—C20—C21	0.7 (7)
N1—N2—C9—C8	−10.4 (4)	C19—C20—C21—C22	−0.6 (7)
C17—N2—C9—C8	176.3 (3)	C20—C21—C22—C17	−0.3 (6)
C7—C8—C9—N2	9.7 (3)	C18—C17—C22—C21	1.2 (5)
C7—C8—C9—C10	−110.7 (3)	N2—C17—C22—C21	−179.1 (3)