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

Jia Hao Goh; Hoong-Kun Fun; Nithinchandra; B Kalluraya; N Satheesh Rai

doi:10.1107/S1600536810011931

. 2010 Apr 14;66(Pt 5):o1063–o1064. doi: 10.1107/S1600536810011931

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

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

PMCID: PMC2979246 PMID: 21579120

Abstract

In the title compound, C₂₁H₁₄ClN₃O₅, an intramolecular C—H⋯O hydrogen bond generates an S(7) ring motif and the furan and pyrazole rings are almost coplanar, making a dihedral angle of 1.98 (5)°. The pyrazole ring is inclined at dihedral angles of 47.59 (4) and 7.27 (4)° to the chlorophenyl and methoxyphenyl groups, respectively. The nitro group is almost coplanar to its attached furan ring [dihedral angle = 2.03 (12)°]. In the crystal, intermolecular C—H⋯O hydrogen bonds link the molecules into a three-dimensional network. The crystal structure also features short intermolecular O⋯N [2.8546 (12) Å] and Cl⋯O [3.0844 (9) Å] contacts as well as aromatic π–π stacking interactions [centroid–centroid distance = 3.4367 (6) Å].

Related literature

For general background to and applications of the title compound, see: Hedge et al. (2006 ▶); Kalluraya et al. (1994 ▶); Rai & Kalluraya (2006 ▶); Rai et al. (2008 ▶). For graph-set theory, see: Bernstein et al. (1995 ▶). For closely related structures, see: Goh et al. (2009a ▶,b ▶, 2010 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₁H₁₄ClN₃O₅
M _r = 423.80
Triclinic,
a = 9.5589 (8) Å
b = 9.6603 (8) Å
c = 10.6401 (9) Å
α = 95.523 (2)°
β = 91.074 (2)°
γ = 107.706 (2)°
V = 930.44 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 100 K
0.35 × 0.30 × 0.15 mm

Data collection

Bruker SMART APEX DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.919, T _max = 0.963
31674 measured reflections
8076 independent reflections
7107 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.146
S = 1.13
8076 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.70 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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/S1600536810011931/hb5382sup1.cif

e-66-o1063-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810011931/hb5382Isup2.hkl

e-66-o1063-Isup2.hkl^{(395.1KB, 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	2.27	2.9153 (12)	126
C2—H2A⋯O5ⁱ	0.93	2.48	3.2820 (13)	145
C14—H14A⋯O4ⁱⁱ	0.93	2.46	3.3846 (12)	175
C21—H21A⋯O2ⁱⁱⁱ	0.96	2.55	3.5064 (14)	173

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors 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 (Hedge et al., 2006). In continuation of our studies on 1,3-dipolar cycloaddition reactions of sydnones with dipolarphiles carrying nitrofuran moiety (Kalluraya et al., 1994), we herein report the crystal structure of the above pyrazole compound.

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 0.003 (1) and 0.004 (1) Å, respectively, at atoms O1 and N2. These two rings are coplanar to one another, making a dihedral angle of 3.06 (10)° between them. The pyrazole ring is inclined at dihedral angles of 47.59 (4) and 7.27 (4)°, respectively, with the mean planes through 4-chlorophenyl (C1-C6/Cl1) and 4-methoxyphenyl (C15-C20/O3/C21) groups. The nitro group is coplanar with the attached furan ring, as indicated by the dihedral angle formed of 2.03 (12)°. The bond lengths and angles are comparable to those observed in closely related pyrazole structures (Goh et al., 2009a,b, 2010).

In the crystal structure, intermolecular C2—H2A···O5, C14—H14A···O4 and C21—H21A···O2 hydrogen bonds (Table 1) link neighbouring molecules into a three-dimensional extended network. The interesting feature of the crystal structure is the short intermolecular Cl1···O3 [3.0844 (9) Å, symmetry code: -x+3, -y+2, -z+1] and O2···N3 [2.8546 (12) Å, symmetry code: -x+1, -y+1, -z+1] interactions which are shorter than the sum of the van der Waals radii of the relevant atoms. The crystal structure is further stabilized by the weak intermolecular π–π interactions involving the pyrazole ring [Cg1···Cg1 = 3.4367 (6) Å; symmetry code: -x+2, -y+1, -z+1].

Experimental

3-(p-Anisyl)sydnone (0.01 mol) and 1-(p-chlorophenyl)-3-(5-nitro-2-furyl)-2-propyn-1-one (0.01 mol) were dissolved in dry xylene (10 ml) 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 a mixture of ethanol and DMF. The solid obtained was collected by filtration, washed with ethanol and dried. Orange blocks of (I) were obtained from a 1:2 mixture of ethanol and DMF by slow evaporation.