(4Z)-4-[(2-Chloro­anilino)(phen­yl)methyl­idene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Li-Ying Xu; Ning Li; Jia-Min Li; Heng-Qiang Zhang; Zhen-Hai Sun

doi:10.1107/S1600536812020004

. 2012 May 23;68(Pt 6):o1843. doi: 10.1107/S1600536812020004

(4Z)-4-[(2-Chloroanilino)(phenyl)methylidene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Li-Ying Xu ^a,^b, Ning Li ^a,^*, Jia-Min Li ^c, Heng-Qiang Zhang ^d, Zhen-Hai Sun ^b

PMCID: PMC3379412 PMID: 22719610

Abstract

The title compound, C₂₃H₁₈ClN₃O, exists in an enamine–keto form with the amino group involved in an intramolecular N—H⋯O hydrogen bond. The five-membered ring is nearly planar, the largest deviation being 0.0004 (7) Å, and makes dihedral angles of 16.62 (6), 41.89 (5) and 71.27 (4)° with the phenyl rings. In the crystal, weak C—H⋯O hydrogen bonds link the molecules into supramolecular chains along the b axis.

Related literature

For general background to Schiff bases derived from 1-phenyl-3-methyl-4-benzoyl-1H-pyrazol-5(4H)-one and their pharmaceutical and agrochemical applications, see: Casas et al. (2007 ▶); Zhang et al. (2008 ▶). For related structures, see: Zhang et al. (2007 ▶); Li et al. (2009 ▶); Chi et al. (2010 ▶). graphic file with name e-68-o1843-scheme1.jpg

Experimental

Crystal data

C₂₃H₁₈ClN₃O
M _r = 387.85
Monoclinic,
a = 9.0425 (3) Å
b = 18.5180 (7) Å
c = 11.1983 (4) Å
β = 90.423 (1)°
V = 1875.09 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 296 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.951, T _max = 0.959
17018 measured reflections
4637 independent reflections
4251 reflections with I > 2σ(I)
R _int = 0.013

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.095
S = 1.04
4613 reflections
258 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); 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 datablock(s) I, global. DOI: 10.1107/S1600536812020004/zq2164sup1.cif

e-68-o1843-sup1.cif^{(21.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812020004/zq2164Isup2.hkl

e-68-o1843-Isup2.hkl^{(226KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812020004/zq2164Isup3.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
N3—H3A⋯O1	0.879 (18)	1.915 (18)	2.6800 (14)	144.5 (16)
C6—H6⋯O1	0.93	2.31	2.9027 (16)	121
C16—H16⋯O1ⁱ	0.93	2.56	3.4797 (17)	170

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Scientific Research Foundation of the Education Department of Heilongjiang Province (grant No. 12513059), the Youth Foundation of Harbin University (grant No. HXKQ200610) and the Fundamental Research Funds for the Central Universities (grant No. DL11BB28).

supplementary crystallographic information

Comment

The 1-phenyl-3-methyl-4-benzoyl-1H-pyrazol-5(4H)-ones (PMBP) are a novel type of β-enaminoketone. The Schiff bases derived from PMBP have attracted much attention due to their applications in pharmaceutical and agrochemical fields (e.g. Casas et al., 2007; Zhang et al., 2008). In order to expand this field, we now report the synthesis and structure of the title compound.

The molecular structure of the title compound is shown in Fig.1. Atoms O1, C10, C9 and C11 of the PMBP moiety and atom N3 of the o-chloroaniline group are coplanar, the largest deviation being 0.038 (11) Å for atom C10. The dihedral angle between this mean plane and the pyrazole ring of PMBP is 5.76 (3)°. The C9—C11 bond length of 1.3887 (15) Å, between usual C—C and C=C bond, indicates the delocalization of the electrons because of the addition of a proton to N3 is more favorable than to O2. The atom O2 of the PMBP moiety and the N3 atom of the o-chloroaniline group are on the same side of the C9—C11 bond, which are available for coordination with metal cations. A strong intramolecular hydrogen bond N3—H3A···O1 (Table 1) is also indicative of the enamine-keto form. In the crystal structure, the intramolecular hydrogen bond C6—H6···O1 and intermolecular hydrogen bond C16—H16···O1 are observed, the latter links the molecules into supramolecular chains along the b axis. All bond lengths and angles are normal and comparable with those found in related compounds (Zhang et al., 2007; Li et al., 2009; Chi et al., 2010).

Experimental

A mixture of a 10 ml PMBP (2 mmol, 0.5566 g) anhydrous ethanol solution, and a 0.21 ml of an o-chloroaniline (2 mmol, 0.2545 g) solution was refluxed for ca 5 h, with addition of a few drops of glacial acetic acid as a catalyst. The ethanol was removed by evaporation and the resulting green precipitate formed was filtered off, washed with cold anhydrous ethanol and dried in air. Yellow block single crystals suitable for analysis were obtained by slow evaporation of a solution in anhydrous ethanol at room temperature for a few days.