2-[(5-Amino-3-methyl-1-phenyl-1H-pyrazol-4-yl)(4-chloro­phen­yl)meth­yl]malononitrile

Xin-Ying Zhang; Xiao-Yan Li; Xia Wang; Dong-Fang Li; Xue-Sen Fan

doi:10.1107/S1600536808011562

. 2008 Apr 26;64(Pt 5):o908. doi: 10.1107/S1600536808011562

2-[(5-Amino-3-methyl-1-phenyl-1H-pyrazol-4-yl)(4-chlorophenyl)methyl]malononitrile

Xin-Ying Zhang ^a,^*, Xiao-Yan Li ^a, Xia Wang ^a, Dong-Fang Li ^a, Xue-Sen Fan ^a,^*

PMCID: PMC2961285 PMID: 21202390

Abstract

In the crystal structure of the title compound, C₂₀H₁₆ClN₅, the dihedral angle between the pyrazole ring and the phenyl ring is 54.7 (1)° and that between the pyrazole ring and the chloro-substituted phenyl ring is 72.4 (1)°. The methyl H atoms are disordered over two positions with site occupancy factors of ca 0.7 and 0.3. One amino H is disordered equally over two positions. In the crystal structure, the molecules are linked via intermolecular N—H⋯N hydrogen bonding.

Experimental

Crystal data

C₂₀H₁₆ClN₅
M _r = 361.83
Orthorhombic,
a = 10.4700 (11) Å
b = 14.0482 (15) Å
c = 25.409 (3) Å
V = 3737.3 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 294 (2) K
0.49 × 0.48 × 0.45 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.901, T _max = 0.908
32456 measured reflections
4661 independent reflections
3055 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.118
S = 1.03
4661 reflections
237 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; 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/S1600536808011562/nc2101sup1.cif

e-64-0o908-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808011562/nc2101Isup2.hkl

e-64-0o908-Isup2.hkl^{(228.4KB, 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
N3—H1N3⋯N4ⁱ	0.86	2.41	3.159 (2)	146
N3—H2N3⋯N2ⁱⁱ	0.86	2.53	3.325 (2)	155

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 20772025), the Program for Science & Technology Innovation Talents in Universities of Henan Province (No. 2008HASTIT006) and the Department of Education of Henan Province (No. 2008 A150013).

supplementary crystallographic information

Comment

The structure determination was undertaken as a part of a project on the synthesis of new pyrazole derivatives. In the title compound the dihedral angle between the pyrazole ring and the non-substituted phenyl ring which is directly connected to the pyrazole ring is 54.7 (1)° and that between the pyrazole ring and the chloro-substituted phenyl ring is 72.4 (1)°. The dihedral angle between the non-substituted and the chloro-substituted phenyl ring amount to 69.7 (1)° (Fig. 1).

In the crystal structure the molecules are connected via intermolecular N—H···N hydrogen bonding between the amino group at N3 and the N atoms N2 and N4 (Fig. 2 and Table 1).

Experimental

To 1 ml of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), 4-chloroaldehyde (1 mmol), malononitrile (1 mmol) and 5-amino-3-methyl-1-phenylpyrazole (1 mmol) were added. The reaction mixture was stirred at room temperature for 4 h and afterwards extracted five times with 2 ml of diethylether. The ether extracts were combined and concentrated. The obtained residue was recrystallized with 95% ethanol to give the product in a yield of 95% as white solid. Single crystals of the title compound were obtained by slow evaporation of the solvent from a petroleum ether-ethyl ether (1:1 v/v) solution.