5-(2-Fur­yl)-3-methyl-1-(3-nitro­phen­yl)-4,5-dihydro-1H-pyrazole

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

doi:10.1107/S1600536809031419

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2147

doi:10.1107/S1600536809031419

Open

access

5-(2-Furyl)-3-methyl-1-(3-nitrophenyl)-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 10 August 2009; online 15 August 2009)

In the title compound, C₁₄H₁₃N₃O₃, the pyrazoline ring assumes an envelope conformation with the furanyl-bearing C atom at the flap position. The dihedral angle between the furan and nitrobenzene rings is 84.40 (9)°. 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

C₁₄H₁₃N₃O₃
M_r = 271.27
Triclinic, $[P \overline 1]$
a = 6.2089 (2) Å
b = 7.8581 (3) Å
c = 14.3800 (4) Å
α = 105.764 (2)°
β = 97.054 (2)°
γ = 96.944 (2)°
V = 661.31 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.31 × 0.15 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
9707 measured reflections
2590 independent reflections
1778 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.121
S = 1.10
2590 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.14 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
C12—H12A⋯O1ⁱ	0.93	2.51	3.311 (2)	144
Symmetry code: (i) -x+2, -y+1, -z+1.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; 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/S1600536809031419/xu2580sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809031419/xu2580Isup2.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 new title compound (I) are synthesized in our group.

The pyrazoline ring assumes an envelope conformation with the furanyl-bearing carbon atom at the flap position (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, furylideneacetone (1 mmol, 0.136 g) in ethanol (8 mm l) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized from methanol, bronze single crystals of (I) were obtained after 3 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 title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Packing of (I), showing the intermolecular hydrogen bonds as dashed lines.

5-(2-Furyl)-3-methyl-1-(3-nitrophenyl)-4,5-dihydro-1H-pyrazole top

Crystal data top

C₁₄H₁₃N₃O₃	Z = 2
M_r = 271.27	F(000) = 284
Triclinic, P1	D_x = 1.362 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2089 (2) Å	Cell parameters from 1598 reflections
b = 7.8581 (3) Å	θ = 3.5–24.6°
c = 14.3800 (4) Å	µ = 0.10 mm⁻¹
α = 105.764 (2)°	T = 296 K
β = 97.054 (2)°	Block, bronze
γ = 96.944 (2)°	0.31 × 0.15 × 0.10 mm
V = 661.31 (4) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1778 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.036
Graphite monochromator	θ_max = 26.0°, θ_min = 3.5°
ω scans	h = −7→7
9707 measured reflections	k = −8→9
2590 independent reflections	l = −17→17

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0608P)²] where P = (F_o² + 2F_c²)/3
2590 reflections	(Δ/σ)_max = 0.003
181 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₄H₁₃N₃O₃	γ = 96.944 (2)°
M_r = 271.27	V = 661.31 (4) Å³
Triclinic, P1	Z = 2
a = 6.2089 (2) Å	Mo Kα radiation
b = 7.8581 (3) Å	µ = 0.10 mm⁻¹
c = 14.3800 (4) Å	T = 296 K
α = 105.764 (2)°	0.31 × 0.15 × 0.10 mm
β = 97.054 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1778 reflections with I > 2σ(I)
9707 measured reflections	R_int = 0.036
2590 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 1.10	Δρ_max = 0.14 e Å⁻³
2590 reflections	Δρ_min = −0.21 e Å⁻³
181 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
O	0.36743 (18)	0.34679 (15)	0.90208 (8)	0.0586 (3)
N1	0.1661 (2)	0.62239 (17)	0.78604 (10)	0.0496 (4)
N2	0.2000 (2)	0.45740 (16)	0.72794 (10)	0.0491 (4)
C9	0.3755 (2)	0.4521 (2)	0.67745 (11)	0.0429 (4)
C14	0.5059 (2)	0.6102 (2)	0.67820 (11)	0.0460 (4)
H14A	0.4772	0.7211	0.7132	0.055*
C7	0.0168 (3)	0.5942 (2)	0.83623 (13)	0.0534 (4)
C10	0.4224 (3)	0.2892 (2)	0.62195 (12)	0.0546 (4)
H10A	0.3347	0.1826	0.6191	0.066*
C4	0.2531 (2)	0.2318 (2)	0.81601 (12)	0.0477 (4)
C13	0.6784 (2)	0.5987 (2)	0.62600 (12)	0.0514 (4)
N3	0.8105 (2)	0.7665 (2)	0.62761 (12)	0.0680 (5)
O1	0.9707 (2)	0.7615 (2)	0.58611 (11)	0.0934 (5)
C5	0.0941 (2)	0.3072 (2)	0.75855 (12)	0.0508 (4)
H5A	0.0138	0.2126	0.7010	0.061*
C12	0.7298 (3)	0.4395 (3)	0.57272 (12)	0.0611 (5)
H12A	0.8487	0.4365	0.5391	0.073*
C6	−0.0684 (3)	0.4007 (3)	0.81836 (14)	0.0615 (5)
H6A	−0.2166	0.3686	0.7817	0.074*
H6B	−0.0677	0.3706	0.8795	0.074*
C1	0.4967 (3)	0.2476 (3)	0.94299 (14)	0.0607 (5)
H1B	0.5924	0.2920	1.0022	0.073*
O2	0.7571 (3)	0.9062 (2)	0.67000 (14)	0.1046 (6)
C11	0.5976 (3)	0.2848 (3)	0.57136 (13)	0.0642 (5)
H11A	0.6270	0.1748	0.5355	0.077*
C3	0.3090 (3)	0.0707 (2)	0.80439 (14)	0.0660 (5)
H3A	0.2550	−0.0308	0.7518	0.079*
C2	0.4665 (3)	0.0818 (3)	0.88708 (14)	0.0673 (5)
H2A	0.5350	−0.0108	0.8992	0.081*
C8	−0.0654 (3)	0.7433 (3)	0.90245 (15)	0.0793 (6)
H8A	0.0141	0.8556	0.9019	0.119*
H8B	−0.0444	0.7329	0.9678	0.119*
H8C	−0.2191	0.7381	0.8806	0.119*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O	0.0577 (7)	0.0535 (7)	0.0622 (8)	0.0133 (5)	0.0000 (6)	0.0156 (6)
N1	0.0513 (8)	0.0481 (8)	0.0555 (8)	0.0152 (6)	0.0159 (6)	0.0190 (7)
N2	0.0507 (7)	0.0414 (7)	0.0613 (9)	0.0090 (6)	0.0178 (6)	0.0206 (7)
C9	0.0443 (8)	0.0457 (9)	0.0417 (9)	0.0103 (7)	0.0050 (7)	0.0172 (7)
C14	0.0459 (8)	0.0467 (9)	0.0464 (9)	0.0077 (7)	0.0087 (7)	0.0147 (7)
C7	0.0454 (8)	0.0673 (11)	0.0568 (10)	0.0186 (8)	0.0109 (8)	0.0284 (9)
C10	0.0639 (10)	0.0459 (10)	0.0528 (10)	0.0079 (8)	0.0105 (8)	0.0125 (8)
C4	0.0474 (8)	0.0414 (9)	0.0544 (10)	0.0009 (7)	0.0061 (7)	0.0179 (8)
C13	0.0452 (9)	0.0591 (10)	0.0501 (10)	0.0017 (8)	0.0074 (7)	0.0191 (8)
N3	0.0584 (9)	0.0749 (12)	0.0685 (10)	−0.0040 (8)	0.0163 (8)	0.0210 (9)
O1	0.0729 (9)	0.1114 (12)	0.0966 (11)	−0.0083 (8)	0.0418 (8)	0.0290 (9)
C5	0.0440 (8)	0.0488 (9)	0.0621 (10)	−0.0003 (7)	0.0046 (7)	0.0256 (8)
C12	0.0591 (10)	0.0759 (13)	0.0516 (11)	0.0182 (9)	0.0200 (8)	0.0159 (9)
C6	0.0403 (8)	0.0813 (13)	0.0765 (12)	0.0102 (8)	0.0121 (8)	0.0440 (11)
C1	0.0531 (10)	0.0751 (13)	0.0613 (11)	0.0207 (9)	0.0076 (8)	0.0285 (10)
O2	0.0990 (12)	0.0602 (9)	0.1522 (16)	−0.0069 (8)	0.0581 (11)	0.0187 (10)
C11	0.0777 (12)	0.0602 (11)	0.0550 (11)	0.0230 (10)	0.0176 (10)	0.0093 (9)
C3	0.0813 (13)	0.0457 (10)	0.0690 (13)	0.0129 (9)	0.0027 (10)	0.0164 (9)
C2	0.0761 (12)	0.0621 (13)	0.0761 (13)	0.0288 (10)	0.0118 (10)	0.0333 (11)
C8	0.0778 (13)	0.0996 (16)	0.0771 (14)	0.0422 (12)	0.0352 (11)	0.0316 (12)

Geometric parameters (Å, º) top

O—C4	1.3689 (18)	N3—O2	1.208 (2)
O—C1	1.372 (2)	N3—O1	1.2209 (19)
N1—C7	1.277 (2)	C5—C6	1.532 (2)
N1—N2	1.3940 (18)	C5—H5A	0.9800
N2—C9	1.3803 (19)	C12—C11	1.376 (3)
N2—C5	1.4784 (19)	C12—H12A	0.9300
C9—C14	1.396 (2)	C6—H6A	0.9700
C9—C10	1.397 (2)	C6—H6B	0.9700
C14—C13	1.379 (2)	C1—C2	1.309 (2)
C14—H14A	0.9300	C1—H1B	0.9300
C7—C8	1.482 (2)	C11—H11A	0.9300
C7—C6	1.489 (3)	C3—C2	1.420 (2)
C10—C11	1.380 (2)	C3—H3A	0.9300
C10—H10A	0.9300	C2—H2A	0.9300
C4—C3	1.325 (2)	C8—H8A	0.9600
C4—C5	1.488 (2)	C8—H8B	0.9600
C13—C12	1.375 (2)	C8—H8C	0.9600
C13—N3	1.459 (2)

C4—O—C1	105.97 (13)	C4—C5—H5A	110.0
C7—N1—N2	108.34 (13)	C6—C5—H5A	110.0
C9—N2—N1	118.80 (12)	C13—C12—C11	117.03 (16)
C9—N2—C5	125.31 (13)	C13—C12—H12A	121.5
N1—N2—C5	111.64 (12)	C11—C12—H12A	121.5
N2—C9—C14	120.55 (14)	C7—C6—C5	103.00 (13)
N2—C9—C10	120.96 (14)	C7—C6—H6A	111.2
C14—C9—C10	118.47 (14)	C5—C6—H6A	111.2
C13—C14—C9	118.59 (15)	C7—C6—H6B	111.2
C13—C14—H14A	120.7	C5—C6—H6B	111.2
C9—C14—H14A	120.7	H6A—C6—H6B	109.1
N1—C7—C8	121.87 (16)	C2—C1—O	110.60 (15)
N1—C7—C6	113.46 (15)	C2—C1—H1B	124.7
C8—C7—C6	124.64 (16)	O—C1—H1B	124.7
C11—C10—C9	120.67 (16)	C12—C11—C10	121.50 (17)
C11—C10—H10A	119.7	C12—C11—H11A	119.3
C9—C10—H10A	119.7	C10—C11—H11A	119.3
C3—C4—O	109.50 (15)	C4—C3—C2	107.27 (16)
C3—C4—C5	134.10 (17)	C4—C3—H3A	126.4
O—C4—C5	116.37 (14)	C2—C3—H3A	126.4
C12—C13—C14	123.72 (16)	C1—C2—C3	106.65 (16)
C12—C13—N3	119.04 (15)	C1—C2—H2A	126.7
C14—C13—N3	117.24 (15)	C3—C2—H2A	126.7
O2—N3—O1	122.13 (17)	C7—C8—H8A	109.5
O2—N3—C13	118.76 (15)	C7—C8—H8B	109.5
O1—N3—C13	119.11 (17)	H8A—C8—H8B	109.5
N2—C5—C4	112.93 (12)	C7—C8—H8C	109.5
N2—C5—C6	100.18 (13)	H8A—C8—H8C	109.5
C4—C5—C6	113.50 (14)	H8B—C8—H8C	109.5
N2—C5—H5A	110.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O1ⁱ	0.93	2.51	3.311 (2)	144

Symmetry code: (i) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃N₃O₃
M_r	271.27
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.2089 (2), 7.8581 (3), 14.3800 (4)
α, β, γ (°)	105.764 (2), 97.054 (2), 96.944 (2)
V (Å³)	661.31 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.31 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9707, 2590, 1778
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.121, 1.10
No. of reflections	2590
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.21

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
C12—H12A···O1ⁱ	0.93	2.51	3.311 (2)	144

Symmetry code: (i) −x+2, −y+1, −z+1.

References

Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. 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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2147

doi:10.1107/S1600536809031419

Open

access