Dimethyl 1-(4-cyano­benz­yl)-1H-pyrazole-3,5-dicarboxyl­ate

Jie Xiao; Hong Zhao

doi:10.1107/S1600536809015578

. 2009 Apr 30;65(Pt 5):o1175. doi: 10.1107/S1600536809015578

Dimethyl 1-(4-cyanobenzyl)-1H-pyrazole-3,5-dicarboxylate

Jie Xiao ^a, Hong Zhao ^a,^*

PMCID: PMC2977840 PMID: 21583977

Abstract

The title compound, C₁₅H₁₃N₃O₄, was synthesized from dimethyl 1H-pyrazole-3,5-dicarboxylate and 4-(bromomethyl)benzonitrile. The interplanar angle between the pyrazole and cyanobenzyl ring planes is 71.74 (17)° and an intramolecular C—H⋯O interaction occurs. The crystal structure is stabilized by π–π stacking interactions between the neighbouring pyrazole and benzene rings [centroid–centroid distances of 3.5074 (16) and 3.9401 (15) Å, respectively]. One of the methyl groups is disordered over two positions of equal occupancy.

Related literature

For the biological activity of pyrazoles, see: Chambers et al. (1985 ▶); Lee et al. (1989 ▶). Nitrile derivatives are important materials in the synthesis of some heterocyclic molecules (Radl et al., 2000 ▶). For related structures, see: Dai et al. (2008 ▶); Fu & Zhao (2007 ▶); Xiao & Zhao (2008a ▶,b ▶,c ▶).

Experimental

Crystal data

C₁₅H₁₃N₃O₄
M _r = 299.28
Triclinic,
a = 7.4981 (13) Å
b = 9.1753 (9) Å
c = 12.2884 (18) Å
α = 69.820 (5)°
β = 88.900 (6)°
γ = 68.818 (5)°
V = 734.51 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 292 K
0.35 × 0.30 × 0.25 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.968, T _max = 0.975
7543 measured reflections
3330 independent reflections
1972 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.161
S = 1.03
3330 reflections
202 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015578/fb2152sup1.cif

e-65-o1175-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809015578/fb2152Isup2.hkl

e-65-o1175-Isup2.hkl^{(163.3KB, 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
C6—H6A⋯O2	0.97	2.38	2.966 (3)	119
C14—H14A⋯O4ⁱ	0.96	2.41	3.312 (4)	156

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported financially by Southeast University for Young Researchers (4007041027).

supplementary crystallographic information

Comment

Pyrazole-related molecules have attracted considerable attention due to their biological activities (Lee et al., 1989; Chambers et al., 1985). In addition, the nitrile derivatives are important materials in the synthesis of some heterocyclic molecules (Radl et al., 2000). Recently, we have reported a few benzonitrile compounds (Dai et al.,2008; Fu et al., 2007; Xiao et al.,2008a, 2008b 2008c). As an extension of our work on the structural characterization of the nitrile compounds, the structure of the title compound is reported here. The bond lengths and angles have normal values. The interplanar angle between the pyrazole and cyanobenzyloxy ring planes is 71.74 (17) °. The crystal structure is stabilized by week interactions: C—H···O interactions, C—H···π-electron ring interactions (Tab. 1) and π-π-electron ring stacking interactions (Tab. 2).

Experimental

1H-pyrazole-3,5-dicarboxylic acid dimethyl ester (0.185 mg, 1 mmol) and 4-(bromomethyl)benzonitrile (0.196 mg, 1 mmol) were dissolved in acetone (10 ml) in the presence of K₂CO₃ (0.138 mg, 1 mmol) and heated under reflux for 1 day. After the mixture had been cooled to room temperature, the solution was filtered and the solvent removed in vacuum to afford a white precipitate of the title compound. Colourless prisms (average size: 0.8×1.2×1.0 mm) suitable for X-ray diffraction were obtained by slow evaporation in 7 days from a solution of 100 mg of the crude product in 15 ml of diethylether.