Methyl N-[(4-chloro­phen­yl)(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-yl­idene)meth­yl]glycinate

Xin Zhang; Meng Huang; Cong Du; Dan Chen

doi:10.1107/S1600536809027858

. 2009 Jul 22;65(Pt 8):o1951–o1952. doi: 10.1107/S1600536809027858

Methyl N-[(4-chlorophenyl)(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-ylidene)methyl]glycinate

Xin Zhang ^a,^*, Meng Huang ^a, Cong Du ^a, Dan Chen ^a

PMCID: PMC2977320 PMID: 21583631

Abstract

The title compound, C₂₀H₁₈ClN₃O₃, is in an enamine–keto form, stabilized by two strong intramolecular N—H⋯O hydrogen bonds. The pyrazole ring is oriented at dihedral angles of 4.13 (3) and 85.60 (3)° with respect to the aromatic rings. The dihedral angle between the aromatic rings is 81.79 (3)°. In the crystal structure, intermolecular C—H⋯O hydrogen bonds link the molecules into double chains, which are further linked by weak C—H⋯π interactions, forming a two-dimensional network.

Related literature

For general background to Schiff base compounds in coordination chemistry, catalysis and enzymatic reactions, magnetism and molecular architectures, see: Habibi et al. (2007 ▶). For the anti-bacterial properties of Schiff bases derived from 4-acyl-5-pyrazolones and their metal complexes, see: Li et al. (1997 ▶, 2004 ▶). For the anti-bacterial and biological activity of amino acid esters, see: Xiong et al. (1993 ▶). For related structures, see: Pettinari et al. (1994 ▶); Wang et al. (2003 ▶); Zhang et al. (2005 ▶); Zhu et al. (2005 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₀H₁₈ClN₃O₃
M _r = 383.82
Triclinic,
a = 9.309 (4) Å
b = 10.222 (4) Å
c = 10.685 (5) Å
α = 86.275 (8)°
β = 82.772 (8)°
γ = 71.749 (5)°
V = 957.6 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 296 K
0.24 × 0.20 × 0.18 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.947, T _max = 0.960
4927 measured reflections
3364 independent reflections
1975 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.075
wR(F ²) = 0.229
S = 1.05
3364 reflections
246 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 ▶) and DIAMOND (Brandenburg & Berndt, 1999 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809027858/hk2736sup1.cif

e-65-o1951-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027858/hk2736Isup2.hkl

e-65-o1951-Isup2.hkl^{(165KB, 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—H3⋯O1	0.86	2.06	2.755 (4)	138
N3—H3⋯O2	0.86	2.29	2.679 (4)	108
C16—H16⋯O1ⁱ	0.93	2.42	3.287 (5)	155
C17—H17⋯O1ⁱⁱ	0.93	2.54	3.359 (4)	147
C20—H20B⋯Cg3ⁱⁱⁱ	0.96	2.69	3.604 (4)	160

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg3 is the centroid of the C12–C17 ring.

supplementary crystallographic information

Comment

Schiff base compounds play an important role in the development of coordination chemistry related to catalysis and enzymatic reactions, magnetism, and molecular architectures [Habibi et al., 2007]. In recent years, the Schiff bases derived from 4-acyl-5-pyrazolones and their metal complexes have been studied widely for their high antibacterial activation [Li et al., 1997, 2004]. Amino acid esters also possess good antibacterial and biological activations [Xiong et al., 1993]. Structures of Schiff bases derived from 4-acyl-5-pyrazolones and amino acid esters and closely related to the title compound have been reported [Zhu et al., 2005; Zhang et al., 2005]. We report herein the crystal structure of the title compound, (I).

In the molecule of the title compound, (I), (Fig. 1) the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6), B (N1/N2/C7/C9/C10) and C (C12-C17) are, of course, planar, and they are oriented at a dihedral angles of A/B = 4.13 (3), A/C = 81.79 (3) and B/C = 85.60 (3) °. Intramolecular N-H···O hydrogen bonds (Table 1) stabilize the enamine-keto form as in 4-{[3,4-dihydro-5-methyl-3-oxo-2-phenyl-2H-pyrazol-4-ylidene]-(phenyl)methyl]amino}-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one, (II) (Wang et al., 2003), and result in the formations of planar five- and six-membered rings: D (O2/N3/C18/C19/H3) and E (O1/N3/C9-C11/H3), in which the dihedral angle between them is D/E = 3.83 (4)°. Ring D is oriented with respect to the adjacent ring B at a dihedral angle of 3.12 (4)°. The dihedral angle between ring B and planar (O1/N3/C9-C11) moiety is 0.94 (3)°, which is reported as 3.56 (3)° in (II).

In the crystal structure, intermolecular C-H···O hydrogen bonds (Table 1) link the molecules into double chains (Fig. 2), in which they are further linked by weak C—H···π interactions (Table 1) to form a two-dimensional network (Fig. 3), in which they may be effective in the stabilization of the structure.

Experimental

The title compound was synthesized by refluxing a mixture of 1-phenyl-3-methyl-4-(p-chlor-benzyl)-5-pyrazolone (15 mmol) (Pettinari et al., 1994) and glycine methyl ester (15 mmol) in ethanol (100 ml) over a steam bath for about 5 h. The product was recrystallized from ethanol, affording pale yellow crystals suitable for X-ray analysis. Analysis calculated for C₂₀H₁₈ClN₃O_3:C 62.58, H 4.73, N 10.95%; found: C 62.55, H 4.70, N 10.91%.