1-[3-(2-Nitro­phen­yl)-5-phenyl-2-pyrazolin-1-yl]ethanone

Guo, H.-M.; Huang, B.-Y.; Qin, X.; Zou, H.-Z.; Jian, F.-F.

doi:10.1107/S1600536810020611

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1587

doi:10.1107/S1600536810020611

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1-[3-(2-Nitrophenyl)-5-phenyl-2-pyrazolin-1-yl]ethanone

Huan-Mei Guo,^a Ben-Yu Huang,^b Xiang Qin,^b Huan-Ze Zou ^b and Fang-Fang Jian ^a ^*

^aMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China, and ^bDepartment of Chemistry & Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: ffjian2008@163.com

(Received 16 May 2010; accepted 31 May 2010; online 5 June 2010)

The title compound, C₁₇H₁₅N₃O₃, was prepared from 1-(2-nitrophenyl)-3-phenylprop-2-en-1-one and hydrazine. The dihedral angle between the benzene and phenyl rings is 74.55 (2)°. The pyrazoline ring is in a slight envelope conformation with the C atom bonded to the phenyl ring forming the flap. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds connect molecules into chains along [100].

Related literature

For the biological activity of pyrazoline and its derivatives, see: Rawal et al. (1963 ); Dhal et al. (1975 ); Lombardino & Ottemes (1981 ); Manna et al. (2002 ). For related structures, see: Guo et al. (2006 ); Fahrni et al. (2003 ); Kimura et al. (1977 ).

Experimental

Crystal data

C₁₇H₁₅N₃O₃
M_r = 309.32
Monoclinic, C c
a = 6.5064 (13) Å
b = 12.385 (3) Å
c = 18.752 (4) Å
β = 98.26 (3)°
V = 1495.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
7203 measured reflections
1710 independent reflections
1354 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.087
S = 1.13
1710 reflections
208 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯O3ⁱ	0.93	2.41	3.293 (4)	157
Symmetry code: (i) x+1, y, z.

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/S1600536810020611/lh5050sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810020611/lh5050Isup2.hkl

checkCIF report

Comment top

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 activities (Lombardino & Ottemes, 1981). 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 herein the crystal structure of the title compound, (I).

In the structure of (I) (Fig. 1), the bond lengths and angles are comparable with those in related structures (Guo et al.,2006; Fahrni et al., 2003; Kimura et al., 1977). The dihehral angle between the benzene and phenyl rings is 74.55 (2)°. The pyrazoline ring is in a slight envelope conformation with atom C13 deviating by 0.158 (4) Å form the essentially planar atoms N1/N2/C14/C15 (rms deviation = 0.003 Å). In the crystal structure, weak intermolecular C—H···O hydrogen bonds connect molecules into chains along [100].

Related literature top

For the biological activity of pyrazoline and its derivatives, see: Rawal et al. (1963); Dhal et al. (1975); Lombardino & Ottemes (1981); Manna et al. (2002). For related structures, see: Guo et al. (2006); Fahrni et al. (2003); Kimura et al. (1977).

Experimental top

3-phenyl-1-(2-nitrophenyl)-2-propen-1-one (0.01 mol) and hydrazine (0.03 mol, 80%) were mixed in acetic acid (30 ml) and stirred under reflux for 6 h; the mixture was then poured into ice-water to afford colourless solids. The solids were filtered off and washed with water until the pH of the solution was about 7.0. Finally, the crystals were dried at room temperature. Single crystals of compound (I) 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 of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level.

1-[3-(2-Nitrophenyl)-5-phenyl-2-pyrazolin-1-yl]ethanone top

Crystal data top

C₁₇H₁₅N₃O₃	F(000) = 648
M_r = 309.32	D_x = 1.374 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1354 reflections
a = 6.5064 (13) Å	θ = 3.3–27.3°
b = 12.385 (3) Å	µ = 0.10 mm⁻¹
c = 18.752 (4) Å	T = 293 K
β = 98.26 (3)°	Bar, colourless
V = 1495.4 (5) Å³	0.22 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1354 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 27.5°, θ_min = 3.3°
ϕ and ω scans	h = −8→7
7203 measured reflections	k = −16→16
1710 independent reflections	l = −24→24

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0483P)² + 0.1147P] where P = (F_o² + 2F_c²)/3
1710 reflections	(Δ/σ)_max < 0.001
208 parameters	Δρ_max = 0.20 e Å⁻³
2 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₇H₁₅N₃O₃	V = 1495.4 (5) Å³
M_r = 309.32	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 6.5064 (13) Å	µ = 0.10 mm⁻¹
b = 12.385 (3) Å	T = 293 K
c = 18.752 (4) Å	0.22 × 0.20 × 0.18 mm
β = 98.26 (3)°

Data collection top

Bruker SMART CCD diffractometer	1354 reflections with I > 2σ(I)
7203 measured reflections	R_int = 0.024
1710 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	2 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.13	Δρ_max = 0.20 e Å⁻³
1710 reflections	Δρ_min = −0.13 e Å⁻³
208 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
C7	0.1900 (3)	0.67920 (17)	0.28552 (12)	0.0384 (5)
N1	−0.1077 (3)	0.79477 (16)	0.27976 (10)	0.0373 (4)
C12	0.2478 (3)	0.68202 (17)	0.36067 (13)	0.0381 (5)
N2	−0.2744 (3)	0.82918 (16)	0.23108 (10)	0.0410 (4)
O3	−0.5900 (3)	0.90449 (18)	0.20896 (11)	0.0596 (5)
C15	0.0046 (3)	0.73132 (18)	0.24741 (12)	0.0376 (5)
C8	0.3234 (4)	0.6223 (2)	0.24684 (14)	0.0455 (5)
H8A	0.2919	0.6180	0.1970	0.055*
N3	0.1191 (3)	0.73560 (17)	0.40852 (11)	0.0455 (5)
O2	−0.0409 (3)	0.69121 (17)	0.41903 (11)	0.0593 (5)
C17	−0.4397 (4)	0.8805 (2)	0.25303 (13)	0.0408 (5)
C16	−0.4249 (4)	0.9042 (2)	0.33180 (14)	0.0485 (6)
H16A	−0.5493	0.9399	0.3411	0.073*
H16B	−0.3075	0.9502	0.3464	0.073*
H16C	−0.4083	0.8379	0.3585	0.073*
C9	0.5016 (4)	0.5720 (2)	0.28093 (17)	0.0520 (6)
H9A	0.5873	0.5345	0.2539	0.062*
C13	−0.2630 (4)	0.7933 (2)	0.15621 (12)	0.0438 (5)
H13A	−0.3902	0.7543	0.1372	0.053*
C1	−0.2353 (4)	0.8890 (2)	0.10825 (11)	0.0427 (5)
C2	−0.4070 (4)	0.9335 (2)	0.06620 (13)	0.0505 (6)
H2A	−0.5363	0.9012	0.0652	0.061*
O1	0.1846 (4)	0.8190 (2)	0.43697 (15)	0.0842 (8)
C11	0.4254 (4)	0.6332 (2)	0.39490 (15)	0.0483 (6)
H11A	0.4595	0.6379	0.4447	0.058*
C10	0.5517 (4)	0.5776 (2)	0.35494 (18)	0.0557 (7)
H10A	0.6709	0.5437	0.3777	0.067*
C14	−0.0785 (5)	0.7133 (2)	0.16914 (13)	0.0533 (6)
H14A	−0.1249	0.6394	0.1605	0.064*
H14B	0.0254	0.7300	0.1385	0.064*
C6	−0.0422 (4)	0.9367 (2)	0.10715 (13)	0.0503 (6)
H6A	0.0754	0.9071	0.1342	0.060*
C5	−0.0242 (5)	1.0285 (3)	0.06587 (15)	0.0595 (7)
H5A	0.1052	1.0603	0.0657	0.071*
C3	−0.3884 (5)	1.0259 (3)	0.02551 (14)	0.0614 (7)
H3A	−0.5054	1.0560	−0.0015	0.074*
C4	−0.1966 (5)	1.0726 (3)	0.02533 (14)	0.0633 (8)
H4A	−0.1836	1.1340	−0.0022	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C7	0.0380 (11)	0.0305 (11)	0.0467 (12)	0.0000 (9)	0.0063 (10)	0.0020 (9)
N1	0.0378 (10)	0.0350 (10)	0.0380 (9)	0.0039 (8)	0.0018 (8)	0.0045 (7)
C12	0.0385 (12)	0.0295 (11)	0.0452 (11)	−0.0034 (9)	0.0027 (10)	−0.0010 (9)
N2	0.0412 (10)	0.0440 (11)	0.0367 (9)	0.0071 (9)	0.0013 (8)	0.0042 (8)
O3	0.0403 (10)	0.0773 (14)	0.0593 (10)	0.0098 (9)	0.0003 (9)	0.0081 (9)
C15	0.0407 (12)	0.0329 (12)	0.0389 (11)	0.0003 (9)	0.0044 (10)	0.0005 (9)
C8	0.0484 (13)	0.0356 (13)	0.0532 (13)	0.0031 (10)	0.0097 (11)	0.0009 (10)
N3	0.0442 (11)	0.0482 (12)	0.0426 (10)	−0.0021 (10)	0.0008 (9)	−0.0013 (9)
O2	0.0479 (10)	0.0729 (13)	0.0590 (11)	−0.0043 (9)	0.0140 (9)	0.0091 (9)
C17	0.0342 (11)	0.0398 (13)	0.0484 (12)	−0.0009 (9)	0.0063 (10)	0.0061 (10)
C16	0.0465 (13)	0.0472 (14)	0.0542 (14)	0.0025 (11)	0.0153 (11)	0.0020 (12)
C9	0.0420 (13)	0.0403 (14)	0.0751 (18)	0.0055 (11)	0.0128 (13)	−0.0027 (12)
C13	0.0474 (14)	0.0434 (13)	0.0381 (12)	0.0024 (10)	−0.0030 (10)	−0.0042 (10)
C1	0.0454 (13)	0.0489 (14)	0.0321 (10)	0.0046 (10)	−0.0006 (10)	−0.0062 (9)
C2	0.0465 (13)	0.0651 (17)	0.0378 (11)	0.0047 (12)	−0.0015 (10)	0.0027 (11)
O1	0.0747 (14)	0.0793 (16)	0.1018 (18)	−0.0201 (12)	0.0239 (13)	−0.0516 (14)
C11	0.0477 (14)	0.0379 (13)	0.0553 (14)	−0.0013 (11)	−0.0065 (11)	0.0005 (11)
C10	0.0402 (13)	0.0409 (14)	0.0829 (19)	0.0066 (12)	−0.0018 (13)	0.0042 (13)
C14	0.0695 (17)	0.0472 (15)	0.0409 (12)	0.0148 (13)	−0.0004 (12)	−0.0066 (10)
C6	0.0459 (14)	0.0654 (17)	0.0372 (12)	0.0006 (13)	−0.0026 (10)	−0.0036 (11)
C5	0.0654 (17)	0.0661 (18)	0.0475 (13)	−0.0154 (15)	0.0103 (13)	−0.0063 (13)
C3	0.0671 (18)	0.074 (2)	0.0427 (13)	0.0159 (16)	0.0055 (12)	0.0105 (13)
C4	0.086 (2)	0.0612 (19)	0.0443 (14)	−0.0036 (16)	0.0155 (15)	0.0074 (12)

Geometric parameters (Å, º) top

C7—C8	1.399 (3)	C9—H9A	0.9300
C7—C12	1.406 (3)	C13—C1	1.514 (4)
C7—C15	1.461 (3)	C13—C14	1.548 (4)
N1—C15	1.283 (3)	C13—H13A	0.9800
N1—N2	1.381 (3)	C1—C2	1.386 (3)
C12—C11	1.378 (3)	C1—C6	1.392 (4)
C12—N3	1.471 (3)	C2—C3	1.390 (4)
N2—C17	1.363 (3)	C2—H2A	0.9300
N2—C13	1.484 (3)	C11—C10	1.375 (4)
O3—C17	1.223 (3)	C11—H11A	0.9300
C15—C14	1.506 (3)	C10—H10A	0.9300
C8—C9	1.388 (4)	C14—H14A	0.9700
C8—H8A	0.9300	C14—H14B	0.9700
N3—O1	1.212 (3)	C6—C5	1.390 (4)
N3—O2	1.218 (3)	C6—H6A	0.9300
C17—C16	1.496 (3)	C5—C4	1.374 (4)
C16—H16A	0.9600	C5—H5A	0.9300
C16—H16B	0.9600	C3—C4	1.376 (5)
C16—H16C	0.9600	C3—H3A	0.9300
C9—C10	1.381 (4)	C4—H4A	0.9300

C8—C7—C12	115.8 (2)	N2—C13—H13A	109.7
C8—C7—C15	120.0 (2)	C1—C13—H13A	109.7
C12—C7—C15	124.2 (2)	C14—C13—H13A	109.7
C15—N1—N2	108.84 (18)	C2—C1—C6	118.6 (2)
C11—C12—C7	122.8 (2)	C2—C1—C13	119.7 (2)
C11—C12—N3	115.2 (2)	C6—C1—C13	121.7 (2)
C7—C12—N3	121.9 (2)	C1—C2—C3	120.9 (3)
C17—N2—N1	121.55 (18)	C1—C2—H2A	119.5
C17—N2—C13	125.0 (2)	C3—C2—H2A	119.5
N1—N2—C13	113.05 (17)	C10—C11—C12	119.5 (2)
N1—C15—C7	121.70 (19)	C10—C11—H11A	120.2
N1—C15—C14	113.7 (2)	C12—C11—H11A	120.2
C7—C15—C14	124.5 (2)	C11—C10—C9	120.0 (2)
C9—C8—C7	121.8 (3)	C11—C10—H10A	120.0
C9—C8—H8A	119.1	C9—C10—H10A	120.0
C7—C8—H8A	119.1	C15—C14—C13	102.69 (19)
O1—N3—O2	124.6 (2)	C15—C14—H14A	111.2
O1—N3—C12	117.3 (2)	C13—C14—H14A	111.2
O2—N3—C12	118.0 (2)	C15—C14—H14B	111.2
O3—C17—N2	119.9 (2)	C13—C14—H14B	111.2
O3—C17—C16	123.5 (2)	H14A—C14—H14B	109.1
N2—C17—C16	116.6 (2)	C5—C6—C1	120.3 (2)
C17—C16—H16A	109.5	C5—C6—H6A	119.9
C17—C16—H16B	109.5	C1—C6—H6A	119.9
H16A—C16—H16B	109.5	C4—C5—C6	120.4 (3)
C17—C16—H16C	109.5	C4—C5—H5A	119.8
H16A—C16—H16C	109.5	C6—C5—H5A	119.8
H16B—C16—H16C	109.5	C4—C3—C2	119.9 (3)
C10—C9—C8	120.1 (2)	C4—C3—H3A	120.1
C10—C9—H9A	120.0	C2—C3—H3A	120.1
C8—C9—H9A	120.0	C5—C4—C3	120.0 (3)
N2—C13—C1	110.74 (19)	C5—C4—H4A	120.0
N2—C13—C14	100.74 (17)	C3—C4—H4A	120.0
C1—C13—C14	116.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O3ⁱ	0.93	2.41	3.293 (4)	157

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₅N₃O₃
M_r	309.32
Crystal system, space group	Monoclinic, Cc
Temperature (K)	293
a, b, c (Å)	6.5064 (13), 12.385 (3), 18.752 (4)
β (°)	98.26 (3)
V (Å³)	1495.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.22 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7203, 1710, 1354
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.087, 1.13
No. of reflections	1710
No. of parameters	208
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.13

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
C6—H6A···O3ⁱ	0.93	2.41	3.293 (4)	157

Symmetry code: (i) x+1, y, z.

Acknowledgements

This work was supported by the Natural Science Foundation of Shandong Province (No. Y2008B29), P. R. China, and the Yuandu Scholar Fund of Weifang City.

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