(4-Methyl­phen­yl)[3-(5-nitro-2-fur­yl)-1-phenyl-1H-pyrazol-4-yl]methanone

Jia Hao Goh; Hoong-Kun Fun; Nithinchandra; B Kalluraya

doi:10.1107/S1600536809047217

. 2009 Nov 14;65(Pt 12):o3088–o3089. doi: 10.1107/S1600536809047217

(4-Methylphenyl)[3-(5-nitro-2-furyl)-1-phenyl-1H-pyrazol-4-yl]methanone

Jia Hao Goh ^a,^‡, Hoong-Kun Fun ^a,^*,^§, Nithinchandra ^b, B Kalluraya ^b

PMCID: PMC2972143 PMID: 21578818

Abstract

In the title pyrazole compound, C₂₁H₁₅N₃O₄, an intramolecular C—H⋯O hydrogen bond generates an S(7) ring motif. The essentially planar furan and pyrazole rings [maximum atomic deviations of 0.011 (2) and 0.006 (2) Å, respectively] make a dihedral angle of 9.21 (11)°. The nitro group is approximately coplanar with the attached furan ring, as indicated by the dihedral angle of 4.5 (2)°. In the crystal structure, intermolecular C—H⋯O interactions form bifurcated hydrogen bonds, generating R ¹ ₂(7) ring motifs. These hydrogen bonds link the molecules into infinite chains along the a axis. The crystal structure is further stabilized by weak intermolecular π–π interactions [centroid–centroid distance = 3.4118 (10) Å].

Related literature

For general background to and applications of the title compound, see: Hegde et al. (2006 ▶); Kalluraya et al. (1994 ▶); Rai & Kalluraya (2006 ▶); Rai et al. (2008 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶). graphic file with name e-65-o3088-scheme1.jpg

Experimental

Crystal data

C₂₁H₁₅N₃O₄
M _r = 373.36
Monoclinic,
a = 11.3859 (2) Å
b = 7.5746 (2) Å
c = 21.0008 (4) Å
β = 107.202 (1)°
V = 1730.17 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.19 × 0.18 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.981, T _max = 0.990
22336 measured reflections
5085 independent reflections
2678 reflections with I > 2σ(I)
R _int = 0.085

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.135
S = 1.02
5085 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809047217/fj2257sup1.cif

e-65-o3088-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809047217/fj2257Isup2.hkl

e-65-o3088-Isup2.hkl^{(249.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯O2	0.93	2.24	2.902 (2)	128
C14—H14A⋯O3ⁱ	0.93	2.55	3.467 (2)	168
C20—H20A⋯O3ⁱ	0.93	2.46	3.373 (3)	166

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Symmetry code: (i) Inline graphic .

Acknowledgments

HKF and JHG thank Universiti Sains Malaysia (USM) for the Research University Golden Goose grant (No. 1001/PFIZIK/811012). JHG also thanks USM for the award of a USM fellowship.

supplementary crystallographic information

Comment

The pyrazole nucleus constitutes an interesting class of organic compound with diverse chemical applications. They possess anti-pyretic, anti-tumor, tranquilizing and herbicidal activities. Sydnones are easily accessible aromatic compounds and versatile synthetic intermediates with a masked azomethine imine unit. The 1,3-dipolar cycloaddition reaction with various dipolarophiles offers a convenient synthetic route for the preparation of pyrazole derivatives and has been studied extensively (Rai & Kalluraya, 2006; Rai et al., 2008).

The incorporation of 5-nitrofuran moiety into various heterocyclic systems has found to increase their biological activities. We have reported a few heterocyclic systems carrying 5-nitrofuran moiety as potent anti-microbial agents (Hegde et al., 2006). In continuation of our studies on 1,3-dipolar cycloaddition reactions of sydnones with dipolarophiles carrying nitrofuran moiety (Kalluraya et al., 1994), we herein report the synthesis of this new pyrazole.

In the title pyrazole compound, an intramolecular C11—H11A···O2 hydrogen bond (Table 1) generates a seven-membered ring, producing an S(7) ring motif (Fig. 1, Bernstein et al., 1995). The furan (C10-C13/O1) and pyrazole (C8/C9/N2/N1/C14) rings are essentially planar, with maximum deviations of 0.011 (2) and 0.006 (2) Å, respectively, for atoms C10 and N2. These two rings are slightly twisted to one another, making a dihedral angle of 9.21 (11)° between them. The nitro group is approximately coplanar with the attached furan ring, as shown by the dihedral angle formed between the mean plane through N3/O3/O4 and the C10-C13/O1 furan ring of 4.5 (2)°. The bond lengths (Allen et al., 1987) and angles observed are within normal ranges.

In the crystal structure (Fig. 2), intermolecular C14—H14A···O3 and C20—H20A···O3 interactions (Table 1) form bifurcated acceptor hydrogen bonds which generate R¹₂(7) ring motifs. These hydrogen bonds link the molecules into one-dimensional infinite chains along the a axis. The crystal structure is further stabillized by weak intermolecular π–π interactions [Cg1···Cg1 = 3.4118 (10) Å; Cg1 is the centroid of the C8/C9/N2/N1/C14 pyrazole ring].

Experimental

3-Phenyl sydnone (0.01 mol) and 1-(p-methylphenyl)-3-(5-nitro-2-furyl)-2-propyn-1-one (0.01 mol) were dissolved in 10 ml dry xylene and refluxed for 4 h. After completion of the reaction, the solvent was removed by distillation under reduced pressure. The crude product obtained was purified by recrystallization from ethanol and DMF mixture. The solid obtained was collected by filtration, washed with ethanol and dried. Single crystals suitable for X-ray analysis were obtained from a 1:2 mixture of DMF and ethanol by slow evaporation.