(Z)-1-(2-Chloro­phen­yl)-3-methyl-4-[2-(4-nitro­phen­yl)hydrazin-1-yl­idene]-1H-pyrazol-5(4H)-one

Carlos Bustos; Andrés Escobar-Fuentealba; Luis Alvarez-Thon; Rodrigo Faundez-Gutierrez; Maria Teresa Garland

doi:10.1107/S1600536812029790

. 2012 Jul 7;68(Pt 8):o2351–o2352. doi: 10.1107/S1600536812029790

(Z)-1-(2-Chlorophenyl)-3-methyl-4-[2-(4-nitrophenyl)hydrazin-1-ylidene]-1H-pyrazol-5(4H)-one

Carlos Bustos ^a, Andrés Escobar-Fuentealba ^a, Luis Alvarez-Thon ^b,^*, Rodrigo Faundez-Gutierrez ^a, Maria Teresa Garland ^c

PMCID: PMC3414286 PMID: 22904819

Abstract

There are two independent molecules, A and B, in the asymmetric unit of the title compound, C₁₆H₁₂ClN₅O₃. The relative orientations of the chlorophenyl ring with respect to the pyrazole ring in the two crystallographically independent molecules are different, and their corresponding dihedral angles are −53.3 (2) and 114.09 (18)° in molecules A and B, respectively. There are two strong intramolecular N—H⋯O hydrogen bonds, and two weak intramolecular C—H⋯O and C—H⋯Cl hydrogen bonds. The crystal packing is constructed by weak C—H⋯O and N—H⋯O interactions, and two π–π stacking interactions [centroid–centroid distances = 3.7894 (9) and 3.5719 (10) Å], forming a molecular ladder along the a axis.

Related literature

For synthesis and related literature, see: Abdel-Aziz et al. (2009 ▶); Bustos et al. (2006 ▶, 2007 ▶, 2009 ▶, 2012 ▶). For the biological activity of this class of compounds, see: Castagnolo et al. (2009 ▶); Chauhan et al. (1993 ▶); El-Hawash et al. (2006 ▶); Gunasekaran et al. (2011 ▶); Himly et al. (2003 ▶); Jolly et al. (1991 ▶); Kalluraya et al. (2007 ▶); Kawai et al. (1997 ▶); Moreau et al. (2008 ▶); Pasha et al. (2009 ▶); Radi et al. (2009 ▶); Singh (1991 ▶); Wu et al. (2002 ▶).

Experimental

Crystal data

C₁₆H₁₂ClN₅O₃
M _r = 357.76
Triclinic,
a = 7.2715 (6) Å
b = 14.7757 (12) Å
c = 15.7609 (12) Å
α = 75.408 (1)°
β = 86.943 (1)°
γ = 79.774 (1)°
V = 1612.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 150 K
0.24 × 0.22 × 0.10 mm

Data collection

Bruker D8 Discover diffractometer with SMART CCD area-detector
13022 measured reflections
6469 independent reflections
4430 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.097
S = 0.91
6469 reflections
461 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL-PC (Sheldrick, 2008 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2008 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812029790/ds2200sup1.cif

e-68-o2351-sup1.cif^{(34.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812029790/ds2200Isup2.hkl

e-68-o2351-Isup2.hkl^{(316.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812029790/ds2200Isup3.cml

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
N4—H7⋯O1	0.910 (19)	2.084 (18)	2.777 (2)	132.1 (14)
N9—H8⋯O4	0.863 (19)	2.222 (18)	2.8647 (19)	131.2 (16)
C28—H28⋯O2	0.95	2.57	3.265 (2)	130
C15—H15⋯Cl2	0.95	2.93	3.4770 (18)	118
N9—H8⋯O2	0.86 (2)	2.654 (18)	3.266 (2)	129.0 (13)
N9—H8⋯O1ⁱ	0.863 (19)	2.478 (17)	3.094 (2)	128.9 (14)
C4—H4⋯O5ⁱⁱ	0.95	2.37	3.202 (3)	146
C10—H10B⋯O3ⁱⁱⁱ	0.98	2.52	3.392 (3)	148
C10—H10C⋯O6^iv	0.98	2.43	3.175 (3)	133
C32—H32⋯Cl2^v	0.95	2.80	3.6898 (18)	157

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

Acknowledgments

The authors thank the Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT; grant Nos. 11100446 and 1080269) and the Universidad Andrés Bello (grant No. DI-27-12-R) for financial assistance.

supplementary crystallographic information

Comment

In previous papers, we have informed preliminary results about the synthesis of a large library of pyrazoles by reaction of β-diketohydrazones with substituted arylhydrazines (Bustos et al., 2009) and three molecular structures of this type of compounds have been reported (Bustos et al., 2006, 2007, 2012). As a consequence of these studies we have found that α-hydrazo-β-ketoesters yield pyrazolones by reaction with substituted arylhydrazines. Now, we present the synthesis and the molecular structure of the title compound, prepared by reaction of (E)-ethyl 2-(2-(4-nitrophenyl)hydrazinylidene)-3-oxobutanoate with (2-chlorophenyl)hydrazine.

The title compound shown in Fig. 1, crystallizes with two independent molecules in the asymmetric unit, where the chlorophenyl ring display a different orientation with respect to the pyrazole ring in molecules A and B. The corresponding dihedral angles between the chlorophenyl and pyrazole rings, in molecule A and molecule B are -53.3 (2)° and 114.09 (18)° respectively. In the crystal, two strong intramolecular hydrogen bonds (N4—H7···O1 and N9—H8···O4) are observed (Fig. 1, Table 1). As shown in Fig. 1 and Table 1, there are three additional weak intramolecular contacts that link molecules A and B (N9—H8···O2, C15—H15···Cl2 and C28—H28···O2). The atoms in the C1—C6 ring are slightly disordered due to thermal motion.

The partial packing of (I), shows that the two molecules in the asymmetric unit form inversion dimers via a pair of weak C32—H32···Cl2^v bonds (Fig. 2, Table 1). There is another pair of weak C10—H10B···O3ⁱⁱⁱ bonds that form a dimer involving molecule A. In addition, there are two π–π stacking interactions, one with Cg···Cgⁱ distance of 3.6112 (9) Å and the other with Cg···Cgⁱⁱⁱ distance of 3.7894 (9) Å, where Cg is the centroid of the C11–C16 ring. These interactions form a molecular ladder that runs parallel to the a axis (Fig. 3, Table 1). Finally the crystal packing is completed with three weak contacts: C4—H4···O5ⁱⁱ, N9—H8···O1ⁱ and C10—H10C···O6^iv (Table 1). [Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) x - 1, y + 1, z + 1; (iii) -x + 1, -y + 1, -z + 1; (iv) x, y, z + 1; (v) -x + 1, -y, -z + 1].

Experimental

In a 100 ml round-bottomed flask were added 2.34 g (8.38 mmole) of (E)-ethyl 2-(2-(4-nitrophenyl)hydrazinylidene)-3-oxobutanoate, 1.60 g (8.94 mmole) 2-(2-chlorophenyl)hydrazine hydrochloride, 5 ml of glacial acetic acid and 50 ml of ethanol. The reaction mixture was magnetically stirred and heated under reflux during 36 h. Then, after cooling at room temperature, the precipitate was filtrated by suction and dried in a vacuum oven at 45°C during 24 h. Yield 78% of crude product. Single crystals suitable for X-ray studies were obtained by recrystallization from tetrahydrofuran. Melting point: 182–183 °C.