3-Methyl-1-(3-nitro­phen­yl)-5-phenyl-4,5-dihydro-1H-pyrazole

Chen, J.; Li, H.; Huang, C.; Wu, J.

doi:10.1107/S1600536809031390

organic compounds

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Volume 65| Part 9| September 2009| Page o2156

doi:10.1107/S1600536809031390

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3-Methyl-1-(3-nitrophenyl)-5-phenyl-4,5-dihydro-1H-pyrazole

Jun-qiang Chen,^a ^* He-ping Li,^b Chang-shan Huang ^a and Jin-ying Wu ^a

^aEnergy Research Institute Co Ltd, Henan Academy of Sciences, Zhengzhou 450000, People's Republic of China, and ^bSchool of Chemistry and Biological Engineering, Guilin University of Technology, People's Republic of China
^*Correspondence e-mail: junqiangchen2009@126.com

(Received 6 August 2009; accepted 9 August 2009; online 15 August 2009)

In the title compound, C₁₆H₁₅N₃O₂, the planar [maximum deviation 0.156 (2) Å] pyrazoline ring is nearly coplanar with the 3-nitrophenyl group and is approximately perpendicular to the phenyl ring, making dihedral angles of 3.80 (8) and 80.58 (10)°, respectively. Weak intermolecular C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For applications of pyrazoline derivatives, see: Hatheway et al. (1978 ); Mahajan et al. (1991 ); Sobczak & Pawlaczyk (1998 ).

Experimental

Crystal data

C₁₆H₁₅N₃O₂
M_r = 281.31
Monoclinic, P 2₁ /n
a = 12.0173 (4) Å
b = 7.9324 (2) Å
c = 15.4944 (5) Å
β = 99.160 (2)°
V = 1458.18 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.36 × 0.18 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
10272 measured reflections
3014 independent reflections
1648 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.128
S = 1.00
3014 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14A⋯O1ⁱ	0.93	2.51	3.245 (2)	136
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809031390/xu2579sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809031390/xu2579Isup2.hkl

checkCIF report

Comment top

The derivatives of pyrazoline are mostly used in medicine, for example as antitumor (Hatheway et al., 1978), analgesic (Sobczak & Pawlaczyk, 1998), and antimicrobial (Mahajan et al., 1991) agents. As part of our work, the title compound is recently synthesized in our group and its crystal structure is reported here.

The pyrazoline ring and the 3-nitrophenyl ring are nearly coplanar, making a dihedral angle of 3.80 (8)°, while the dihedral angle between the pyrazoline ring and the C1-phenyl ring is 80.58 (10)° (Fig. 1). Intermolecular weak C—H···O hydrogen bonding is present in the crystal structure (Fig. 2 and Table 1).

Related literature top

For applications of pyrazoline derivatives, see: Hatheway et al. (1978); Mahajan et al. (1991); Sobczak & Pawlaczyk (1998).

Experimental top

3-Nitrophenylhydrazine (1 mmol, 0.153 g) was dissolved in anhydrous ethanol (15 ml). The mixture was stirred for several min at 351 K, benzylideneacetone (1 mmol, 0.146 g) in ethanol (8 ml) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized from methanol, red single crystals were obtained after 2 d.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the compound. The displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Packing of (I), showing the intermolecular hydrogen bonds as dashed lines.

3-Methyl-1-(3-nitrophenyl)-5-phenyl-4,5-dihydro-1H-pyrazole top

Crystal data top

C₁₆H₁₅N₃O₂	F(000) = 592
M_r = 281.31	D_x = 1.281 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1824 reflections
a = 12.0173 (4) Å	θ = 2.6–26.5°
b = 7.9324 (2) Å	µ = 0.09 mm⁻¹
c = 15.4944 (5) Å	T = 296 K
β = 99.160 (2)°	Plate, red
V = 1458.18 (8) Å³	0.36 × 0.18 × 0.07 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1648 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.034
Graphite monochromator	θ_max = 26.5°, θ_min = 2.0°
ω scans	h = −14→15
10272 measured reflections	k = −9→8
3014 independent reflections	l = −18→19

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0621P)²] where P = (F_o² + 2F_c²)/3
3014 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₆H₁₅N₃O₂	V = 1458.18 (8) Å³
M_r = 281.31	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.0173 (4) Å	µ = 0.09 mm⁻¹
b = 7.9324 (2) Å	T = 296 K
c = 15.4944 (5) Å	0.36 × 0.18 × 0.07 mm
β = 99.160 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1648 reflections with I > 2σ(I)
10272 measured reflections	R_int = 0.034
3014 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.00	Δρ_max = 0.14 e Å⁻³
3014 reflections	Δρ_min = −0.20 e Å⁻³
190 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
C11	0.40009 (13)	0.17187 (19)	0.06087 (10)	0.0433 (4)
N2	0.29773 (12)	0.18897 (16)	0.00749 (10)	0.0578 (4)
C15	0.54447 (14)	0.00161 (19)	0.13960 (10)	0.0454 (4)
C7	0.24060 (14)	0.3481 (2)	−0.02008 (11)	0.0535 (5)
H7A	0.2879	0.4156	−0.0529	0.064*
C16	0.44095 (13)	0.01314 (19)	0.08743 (10)	0.0425 (4)
H16A	0.3991	−0.0832	0.0703	0.051*
N1	0.23515 (12)	0.04742 (18)	−0.02230 (9)	0.0548 (4)
C12	0.46581 (14)	0.3125 (2)	0.08824 (11)	0.0519 (5)
H4A	0.4395	0.4197	0.0714	0.062*
C6	0.21138 (13)	0.4493 (2)	0.05545 (11)	0.0472 (4)
C13	0.56934 (14)	0.2941 (2)	0.13993 (12)	0.0561 (5)
H13A	0.6121	0.3895	0.1572	0.067*
N3	0.58488 (14)	−0.1672 (2)	0.16800 (11)	0.0619 (4)
C1	0.21969 (14)	0.6221 (2)	0.05691 (13)	0.0584 (5)
H1B	0.2456	0.6777	0.0111	0.070*
O1	0.67543 (13)	−0.17917 (18)	0.21576 (11)	0.0990 (6)
C14	0.61085 (14)	0.1383 (2)	0.16652 (11)	0.0536 (5)
H14A	0.6809	0.1259	0.2013	0.064*
O2	0.52813 (13)	−0.28871 (17)	0.14279 (11)	0.0905 (5)
C5	0.17261 (15)	0.3710 (3)	0.12393 (13)	0.0650 (5)
H5A	0.1664	0.2542	0.1241	0.078*
C8	0.13676 (16)	0.2830 (2)	−0.08217 (13)	0.0684 (6)
H8A	0.0675	0.3240	−0.0649	0.082*
H8B	0.1391	0.3168	−0.1420	0.082*
C9	0.14648 (15)	0.0972 (2)	−0.07219 (12)	0.0591 (5)
C4	0.14288 (17)	0.4619 (3)	0.19199 (14)	0.0777 (6)
H12A	0.1166	0.4065	0.2377	0.093*
C2	0.19016 (16)	0.7141 (3)	0.12524 (16)	0.0729 (6)
H2A	0.1963	0.8310	0.1255	0.088*
C3	0.15175 (17)	0.6329 (4)	0.19279 (14)	0.0777 (6)
H3A	0.1318	0.6945	0.2391	0.093*
C10	0.06227 (18)	−0.0247 (3)	−0.11675 (16)	0.0957 (8)
H10A	0.0856	−0.1375	−0.1002	0.144*
H10B	0.0567	−0.0124	−0.1789	0.144*
H10C	−0.0098	−0.0029	−0.0999	0.144*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C11	0.0398 (10)	0.0436 (10)	0.0470 (10)	0.0024 (8)	0.0079 (8)	−0.0019 (8)
N2	0.0495 (9)	0.0418 (8)	0.0756 (11)	0.0045 (7)	−0.0098 (8)	−0.0003 (7)
C15	0.0460 (10)	0.0452 (10)	0.0457 (10)	0.0054 (8)	0.0097 (8)	0.0021 (8)
C7	0.0505 (11)	0.0526 (11)	0.0567 (11)	0.0095 (9)	0.0057 (9)	0.0079 (9)
C16	0.0402 (10)	0.0422 (10)	0.0451 (10)	−0.0005 (7)	0.0066 (8)	−0.0016 (7)
N1	0.0486 (9)	0.0553 (9)	0.0586 (10)	−0.0003 (7)	0.0028 (8)	−0.0044 (7)
C12	0.0524 (11)	0.0414 (10)	0.0613 (12)	0.0019 (8)	0.0072 (9)	−0.0004 (8)
C6	0.0393 (10)	0.0503 (11)	0.0509 (11)	0.0056 (8)	0.0044 (8)	0.0076 (8)
C13	0.0483 (11)	0.0520 (11)	0.0669 (13)	−0.0111 (9)	0.0059 (10)	−0.0090 (9)
N3	0.0575 (10)	0.0596 (11)	0.0673 (11)	0.0122 (9)	0.0054 (9)	0.0115 (9)
C1	0.0515 (11)	0.0548 (12)	0.0698 (13)	0.0035 (9)	0.0127 (10)	0.0041 (10)
O1	0.0680 (10)	0.0945 (12)	0.1213 (13)	0.0163 (8)	−0.0254 (10)	0.0320 (9)
C14	0.0414 (10)	0.0600 (12)	0.0576 (12)	0.0024 (9)	0.0020 (9)	−0.0024 (9)
O2	0.0924 (11)	0.0471 (8)	0.1237 (14)	0.0038 (8)	−0.0081 (10)	0.0076 (8)
C5	0.0650 (13)	0.0650 (12)	0.0661 (13)	0.0024 (10)	0.0139 (11)	0.0113 (11)
C8	0.0642 (13)	0.0779 (14)	0.0579 (13)	0.0157 (11)	−0.0064 (10)	−0.0013 (10)
C9	0.0494 (11)	0.0694 (13)	0.0555 (12)	0.0051 (10)	−0.0012 (10)	−0.0062 (10)
C4	0.0732 (15)	0.1004 (19)	0.0631 (15)	0.0073 (13)	0.0215 (12)	0.0091 (13)
C2	0.0633 (13)	0.0636 (13)	0.0913 (17)	0.0054 (11)	0.0102 (13)	−0.0148 (12)
C3	0.0609 (13)	0.1077 (19)	0.0644 (15)	0.0120 (13)	0.0094 (11)	−0.0195 (14)
C10	0.0690 (15)	0.1000 (18)	0.1050 (19)	−0.0036 (12)	−0.0269 (13)	−0.0190 (14)

Geometric parameters (Å, º) top

C11—N2	1.375 (2)	N3—O2	1.2093 (18)
C11—C16	1.390 (2)	N3—O1	1.2185 (19)
C11—C12	1.393 (2)	C1—C2	1.378 (3)
N2—N1	1.3888 (18)	C1—H1B	0.9300
N2—C7	1.4678 (19)	C14—H14A	0.9300
C15—C14	1.371 (2)	C5—C4	1.371 (3)
C15—C16	1.374 (2)	C5—H5A	0.9300
C15—N3	1.468 (2)	C8—C9	1.485 (3)
C7—C6	1.506 (2)	C8—H8A	0.9700
C7—C8	1.539 (2)	C8—H8B	0.9700
C7—H7A	0.9800	C9—C10	1.488 (3)
C16—H16A	0.9300	C4—C3	1.360 (3)
N1—C9	1.275 (2)	C4—H12A	0.9300
C12—C13	1.376 (2)	C2—C3	1.370 (3)
C12—H4A	0.9300	C2—H2A	0.9300
C6—C5	1.373 (2)	C3—H3A	0.9300
C6—C1	1.374 (2)	C10—H10A	0.9600
C13—C14	1.371 (2)	C10—H10B	0.9600
C13—H13A	0.9300	C10—H10C	0.9600

N2—C11—C16	120.49 (14)	C6—C1—H1B	119.5
N2—C11—C12	120.89 (14)	C2—C1—H1B	119.5
C16—C11—C12	118.61 (15)	C15—C14—C13	117.08 (16)
C11—N2—N1	120.35 (13)	C15—C14—H14A	121.5
C11—N2—C7	126.29 (14)	C13—C14—H14A	121.5
N1—N2—C7	113.28 (13)	C4—C5—C6	121.3 (2)
C14—C15—C16	123.67 (15)	C4—C5—H5A	119.4
C14—C15—N3	118.79 (15)	C6—C5—H5A	119.4
C16—C15—N3	117.54 (15)	C9—C8—C7	103.05 (14)
N2—C7—C6	112.85 (14)	C9—C8—H8A	111.2
N2—C7—C8	100.85 (13)	C7—C8—H8A	111.2
C6—C7—C8	113.49 (13)	C9—C8—H8B	111.2
N2—C7—H7A	109.8	C7—C8—H8B	111.2
C6—C7—H7A	109.8	H8A—C8—H8B	109.1
C8—C7—H7A	109.8	N1—C9—C8	114.49 (16)
C15—C16—C11	118.59 (15)	N1—C9—C10	121.42 (18)
C15—C16—H16A	120.7	C8—C9—C10	124.09 (17)
C11—C16—H16A	120.7	C3—C4—C5	120.1 (2)
C9—N1—N2	107.90 (15)	C3—C4—H12A	120.0
C13—C12—C11	120.57 (15)	C5—C4—H12A	120.0
C13—C12—H4A	119.7	C3—C2—C1	119.8 (2)
C11—C12—H4A	119.7	C3—C2—H2A	120.1
C5—C6—C1	118.09 (17)	C1—C2—H2A	120.1
C5—C6—C7	120.62 (16)	C4—C3—C2	119.8 (2)
C1—C6—C7	121.27 (16)	C4—C3—H3A	120.1
C14—C13—C12	121.49 (16)	C2—C3—H3A	120.1
C14—C13—H13A	119.3	C9—C10—H10A	109.5
C12—C13—H13A	119.3	C9—C10—H10B	109.5
O2—N3—O1	122.49 (16)	H10A—C10—H10B	109.5
O2—N3—C15	119.20 (15)	C9—C10—H10C	109.5
O1—N3—C15	118.31 (16)	H10A—C10—H10C	109.5
C6—C1—C2	120.93 (19)	H10B—C10—H10C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···O1ⁱ	0.93	2.51	3.245 (2)	136

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅N₃O₂
M_r	281.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	12.0173 (4), 7.9324 (2), 15.4944 (5)
β (°)	99.160 (2)
V (Å³)	1458.18 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.36 × 0.18 × 0.07

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10272, 3014, 1648
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.128, 1.00
No. of reflections	3014
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.20

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···O1ⁱ	0.93	2.51	3.245 (2)	136

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

References

Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Hatheway, G. J., Hansch, C., Kim, K. H., Milstein, S. R., Schmidt, C. L., Smith, R. N. & Quinn, F. R. (1978). J. Med. Chem. 21, 563–567. CrossRef CAS PubMed Web of Science Google Scholar
Mahajan, R. N., Havaldar, F. H. & Fernandes, P. S. (1991). J. Indian Chem. Soc. 68, 245–246. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sobczak, H. & Pawlaczyk, J. (1998). Acta Pol. Pharm. 55, 279–283. CAS PubMed Google Scholar

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doi:10.1107/S1600536809031390

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