1-Acetyl-3-(4-chloro­phen­yl)-5-(4-fluoro­phen­yl)-2-pyrazoline

Li, J.; Xiao, H.-F.; Yang, J.

doi:10.1107/S1600536808018333

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1391

doi:10.1107/S1600536808018333

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1-Acetyl-3-(4-chlorophenyl)-5-(4-fluorophenyl)-2-pyrazoline

Jian Li,^a ^* Huai-Fen Xiao ^b and Jie Yang ^a

^aDepartment of Educational Science and Technology, Weifang University, Weifang 261061, People's Republic of China, and ^bExperimental Junior Middle School of Changle County, Weifang 261061, People's Republic of China
^*Correspondence e-mail: lijiansdwf@163.com

(Received 18 May 2008; accepted 17 June 2008; online 5 July 2008)

In the title molecule, C₁₇H₁₄ClFN₂O, the mean plane of the pyrazoline ring makes dihedral angles of 18.19 (1) and 83.51 (4)° with the 4-chlorobenzene and 4-fluorobenzene rings, respectively. The two benzene rings make a dihedral angle of 76.11 (2)°. Weak intermolecular C—H⋯O hydrogen bonds help stabilize the crystal structure.

Related literature

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

Experimental

Crystal data

C₁₇H₁₄ClFN₂O
M_r = 316.75
Monoclinic, P 2₁ /c
a = 14.5425 (19) Å
b = 11.3580 (14) Å
c = 9.6494 (13) Å
β = 108.154 (2)°
V = 1514.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 273 (2) K
0.14 × 0.12 × 0.06 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
7793 measured reflections
2676 independent reflections
2077 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.098
S = 1.03
2676 reflections
200 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯O1ⁱ	0.97	2.57	3.425 (2)	147
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808018333/at2570sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018333/at2570Isup2.hkl

checkCIF report

Comment top

Pyrazoline and some of its derivatives demonstrate antiviral (Rawal et al., 1963), antifungal (Dhal et al., 1975), and immunosuppressive (Lombardino & Ottemes, 1981) activities. 1-Acetyl-3,5-diaryl-2-pyrazolines have been found to inhibit monoamine oxidases (Manna et al., 2002). As part of our ongoing investigation of pyrazolines and their metal complexes, we report here the crystal structure of the title compound (I).

In (I) (Fig. 1), all bond lengths and angles are normal (Fahrni et al., 2003; Kimura et al., 1977). The mean plane of pyrazoline ring makes dihedral angles of 18.19 (1)° and 83.51 (4)° with 4-chlorobenzene ring and 4-fluorolbenzene ring, respectively. The dihedral angle between the two benzene rings is 76.11 (2)°. Weak intermolecular C—H···O hydrogen bonds help stabilize the crystal structure (Table 1). The crystal packing of (I) is shown in Fig. 2.

Related literature top

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

Experimental top

1-(4-chlorophenyl)-3-(4-fluorophenyl)-2-propenyl-1-ketone (0.02 mol)and hydrazine (0.02 mol)were mixed in 99.5% acetic acid (40 ml) and stirred in refluxing for 6 h, then the mixture was poured into ice-water to afford colourless solids.The solids were filtrated and washed with water until the pH of solution is about to 7.0. Finally, the solid crystals were dry under room temperature. Single crystals of the title compound suitable for X-ray measurements were obtained by recrystallization from EtOH at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure and atom-labeling scheme for (I), with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. View of the crysytal packing of (I) in the unit cell.

1-Acetyl-3-(4-chlorophenyl)-5-(4-fluorophenyl)-2-pyrazoline top

Crystal data top

C₁₇H₁₄ClFN₂O	F(000) = 656
M_r = 316.75	D_x = 1.389 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2887 reflections
a = 14.5425 (19) Å	θ = 2.9–25.9°
b = 11.3580 (14) Å	µ = 0.27 mm⁻¹
c = 9.6494 (13) Å	T = 273 K
β = 108.154 (2)°	Bar, colourless
V = 1514.5 (3) Å³	0.14 × 0.12 × 0.06 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2077 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 25.1°, θ_min = 2.3°
ϕ and ω scans	h = −17→17
7793 measured reflections	k = −13→11
2676 independent reflections	l = −11→9

Refinement top

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)] = 0.037	H-atom parameters constrained
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0385P)² + 0.4849P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2676 reflections	Δρ_max = 0.20 e Å⁻³
200 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0031 (10)

Crystal data top

C₁₇H₁₄ClFN₂O	V = 1514.5 (3) Å³
M_r = 316.75	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.5425 (19) Å	µ = 0.27 mm⁻¹
b = 11.3580 (14) Å	T = 273 K
c = 9.6494 (13) Å	0.14 × 0.12 × 0.06 mm
β = 108.154 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2077 reflections with I > 2σ(I)
7793 measured reflections	R_int = 0.021
2676 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.03	Δρ_max = 0.20 e Å⁻³
2676 reflections	Δρ_min = −0.21 e Å⁻³
200 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.45884 (5)	0.34606 (6)	0.02764 (8)	0.0949 (3)
F1	0.70769 (11)	−0.14714 (11)	1.10898 (14)	0.0851 (4)
O1	1.00066 (10)	−0.13914 (13)	0.72130 (15)	0.0685 (4)
N1	0.88095 (10)	−0.02205 (13)	0.59652 (15)	0.0491 (4)
N2	0.80952 (10)	0.00960 (13)	0.46876 (15)	0.0477 (4)
C1	0.93307 (15)	−0.17908 (18)	0.4668 (2)	0.0610 (5)
H1A	0.9661	−0.1361	0.4109	0.092*
H1B	0.8660	−0.1873	0.4111	0.092*
H1C	0.9617	−0.2557	0.4898	0.092*
C2	0.94144 (13)	−0.11419 (16)	0.6044 (2)	0.0494 (4)
C3	0.88134 (13)	0.05353 (16)	0.72122 (18)	0.0477 (4)
H3	0.9474	0.0797	0.7730	0.057*
C4	0.82018 (14)	0.15743 (16)	0.64155 (19)	0.0500 (5)
H4A	0.7728	0.1808	0.6881	0.060*
H4B	0.8604	0.2246	0.6373	0.060*
C5	0.77233 (12)	0.10719 (16)	0.49247 (18)	0.0454 (4)
C6	0.83785 (12)	−0.00700 (15)	0.82540 (18)	0.0446 (4)
C7	0.76197 (13)	−0.08590 (17)	0.7766 (2)	0.0530 (5)
H7	0.7404	−0.1070	0.6786	0.064*
C8	0.71794 (15)	−0.13366 (18)	0.8711 (2)	0.0593 (5)
H8	0.6671	−0.1868	0.8382	0.071*
C9	0.75105 (15)	−0.10081 (18)	1.0151 (2)	0.0574 (5)
C10	0.82613 (14)	−0.02457 (17)	1.0681 (2)	0.0537 (5)
H10	0.8474	−0.0044	1.1664	0.064*
C11	0.86977 (13)	0.02200 (16)	0.97206 (18)	0.0481 (4)
H11	0.9215	0.0737	1.0065	0.058*
C12	0.69236 (12)	0.16303 (16)	0.37998 (19)	0.0455 (4)
C13	0.63734 (14)	0.10150 (18)	0.2576 (2)	0.0557 (5)
H13	0.6499	0.0222	0.2473	0.067*
C14	0.56443 (15)	0.15720 (19)	0.1515 (2)	0.0621 (5)
H14	0.5275	0.1154	0.0703	0.075*
C15	0.54634 (13)	0.27427 (18)	0.1657 (2)	0.0588 (5)
C16	0.59780 (14)	0.33572 (18)	0.2860 (3)	0.0630 (6)
H16	0.5842	0.4147	0.2957	0.076*
C17	0.67020 (14)	0.28007 (17)	0.3936 (2)	0.0558 (5)
H17	0.7046	0.3218	0.4764	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0695 (4)	0.0900 (5)	0.1055 (5)	0.0056 (3)	−0.0012 (3)	0.0364 (4)
F1	0.1184 (11)	0.0792 (9)	0.0750 (9)	−0.0204 (8)	0.0552 (8)	0.0010 (7)
O1	0.0622 (9)	0.0758 (10)	0.0578 (9)	0.0125 (7)	0.0045 (7)	0.0014 (7)
N1	0.0505 (8)	0.0581 (9)	0.0370 (8)	0.0056 (7)	0.0111 (7)	−0.0052 (7)
N2	0.0485 (8)	0.0565 (9)	0.0372 (8)	0.0015 (7)	0.0121 (6)	−0.0026 (7)
C1	0.0680 (13)	0.0577 (12)	0.0615 (12)	0.0051 (10)	0.0261 (10)	−0.0078 (10)
C2	0.0464 (10)	0.0528 (11)	0.0501 (11)	−0.0025 (9)	0.0167 (9)	0.0005 (9)
C3	0.0456 (10)	0.0571 (11)	0.0393 (9)	−0.0055 (8)	0.0115 (8)	−0.0086 (8)
C4	0.0573 (11)	0.0502 (11)	0.0437 (10)	−0.0045 (9)	0.0177 (8)	−0.0045 (8)
C5	0.0474 (10)	0.0504 (11)	0.0413 (9)	−0.0051 (8)	0.0180 (8)	−0.0026 (8)
C6	0.0431 (9)	0.0497 (10)	0.0381 (9)	0.0034 (8)	0.0084 (7)	−0.0024 (8)
C7	0.0529 (11)	0.0613 (12)	0.0416 (10)	−0.0062 (9)	0.0098 (8)	−0.0067 (9)
C8	0.0599 (12)	0.0570 (12)	0.0623 (13)	−0.0115 (10)	0.0209 (10)	−0.0044 (10)
C9	0.0710 (13)	0.0546 (12)	0.0542 (12)	0.0017 (10)	0.0302 (10)	0.0049 (9)
C10	0.0666 (12)	0.0541 (11)	0.0388 (10)	0.0037 (10)	0.0142 (9)	−0.0018 (8)
C11	0.0487 (10)	0.0498 (10)	0.0416 (10)	0.0001 (8)	0.0078 (8)	−0.0043 (8)
C12	0.0452 (10)	0.0504 (11)	0.0441 (10)	−0.0035 (8)	0.0188 (8)	0.0003 (8)
C13	0.0609 (12)	0.0519 (11)	0.0513 (11)	−0.0008 (9)	0.0131 (9)	−0.0012 (9)
C14	0.0592 (12)	0.0677 (14)	0.0526 (12)	−0.0076 (10)	0.0075 (10)	0.0003 (10)
C15	0.0450 (11)	0.0608 (13)	0.0685 (13)	−0.0036 (9)	0.0144 (9)	0.0141 (10)
C16	0.0534 (12)	0.0488 (11)	0.0880 (16)	0.0000 (9)	0.0238 (11)	0.0063 (11)
C17	0.0511 (11)	0.0532 (12)	0.0636 (12)	−0.0058 (9)	0.0183 (10)	−0.0062 (10)

Geometric parameters (Å, º) top

Cl1—C15	1.733 (2)	C6—C7	1.385 (2)
F1—C9	1.361 (2)	C7—C8	1.378 (3)
O1—C2	1.220 (2)	C7—H7	0.9300
N1—C2	1.354 (2)	C8—C9	1.373 (3)
N1—N2	1.3893 (19)	C8—H8	0.9300
N1—C3	1.477 (2)	C9—C10	1.362 (3)
N2—C5	1.285 (2)	C10—C11	1.381 (3)
C1—C2	1.490 (3)	C10—H10	0.9300
C1—H1A	0.9600	C11—H11	0.9300
C1—H1B	0.9600	C12—C17	1.384 (3)
C1—H1C	0.9600	C12—C13	1.391 (3)
C3—C6	1.510 (2)	C13—C14	1.377 (3)
C3—C4	1.533 (3)	C13—H13	0.9300
C3—H3	0.9800	C14—C15	1.371 (3)
C4—C5	1.502 (2)	C14—H14	0.9300
C4—H4A	0.9700	C15—C16	1.362 (3)
C4—H4B	0.9700	C16—C17	1.380 (3)
C5—C12	1.465 (2)	C16—H16	0.9300
C6—C11	1.385 (2)	C17—H17	0.9300

C2—N1—N2	122.87 (14)	C8—C7—H7	119.5
C2—N1—C3	124.48 (15)	C6—C7—H7	119.5
N2—N1—C3	112.62 (14)	C9—C8—C7	118.28 (18)
C5—N2—N1	107.76 (14)	C9—C8—H8	120.9
C2—C1—H1A	109.5	C7—C8—H8	120.9
C2—C1—H1B	109.5	F1—C9—C10	118.61 (18)
H1A—C1—H1B	109.5	F1—C9—C8	118.66 (19)
C2—C1—H1C	109.5	C10—C9—C8	122.73 (18)
H1A—C1—H1C	109.5	C9—C10—C11	118.23 (17)
H1B—C1—H1C	109.5	C9—C10—H10	120.9
O1—C2—N1	119.36 (17)	C11—C10—H10	120.9
O1—C2—C1	123.17 (18)	C10—C11—C6	121.12 (17)
N1—C2—C1	117.46 (17)	C10—C11—H11	119.4
N1—C3—C6	112.45 (15)	C6—C11—H11	119.4
N1—C3—C4	100.64 (13)	C17—C12—C13	118.28 (18)
C6—C3—C4	112.75 (14)	C17—C12—C5	120.02 (17)
N1—C3—H3	110.2	C13—C12—C5	121.70 (17)
C6—C3—H3	110.2	C14—C13—C12	120.43 (19)
C4—C3—H3	110.2	C14—C13—H13	119.8
C5—C4—C3	102.19 (14)	C12—C13—H13	119.8
C5—C4—H4A	111.3	C15—C14—C13	119.92 (19)
C3—C4—H4A	111.3	C15—C14—H14	120.0
C5—C4—H4B	111.3	C13—C14—H14	120.0
C3—C4—H4B	111.3	C16—C15—C14	120.72 (19)
H4A—C4—H4B	109.2	C16—C15—Cl1	119.42 (17)
N2—C5—C12	121.50 (16)	C14—C15—Cl1	119.84 (17)
N2—C5—C4	113.79 (16)	C15—C16—C17	119.62 (19)
C12—C5—C4	124.69 (16)	C15—C16—H16	120.2
C11—C6—C7	118.63 (17)	C17—C16—H16	120.2
C11—C6—C3	119.71 (16)	C16—C17—C12	120.97 (19)
C7—C6—C3	121.53 (15)	C16—C17—H17	119.5
C8—C7—C6	120.99 (17)	C12—C17—H17	119.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···O1ⁱ	0.97	2.57	3.425 (2)	147

Symmetry code: (i) −x+2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₄ClFN₂O
M_r	316.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	14.5425 (19), 11.3580 (14), 9.6494 (13)
β (°)	108.154 (2)
V (Å³)	1514.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.14 × 0.12 × 0.06

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7793, 2676, 2077
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.098, 1.03
No. of reflections	2676
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.21

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···O1ⁱ	0.97	2.57	3.425 (2)	146.60

Symmetry code: (i) −x+2, y+1/2, −z+3/2.

Acknowledgements

The authors thank the Sparking Plan of Shandong Province (grant No. 200674006017) and the National Sparking Plan Project (grant No. 2007E740083).

References

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