(4Z)-4-[(4-Methoxy­benzyl­amino)(phen­yl)methyl­ene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Hai-Zhen Xu; Jian-Ping Xu; Jin Zhang; Yan-Wei Yuan; You-Quan Zhu

doi:10.1107/S1600536809040458

. 2009 Oct 17;65(Pt 11):o2740. doi: 10.1107/S1600536809040458

(4Z)-4-[(4-Methoxybenzylamino)(phenyl)methylene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Hai-Zhen Xu ^a,^*, Jian-Ping Xu ^b, Jin Zhang ^c, Yan-Wei Yuan ^c, You-Quan Zhu ^c,^*

PMCID: PMC2971322 PMID: 21578335

Abstract

In the title compound, C₂₅H₂₃N₃O₂, the dihedral angles formed by the pyrazolone ring with the three aromatic rings are 14.59 (7), 79.35 (5) and 87.10 (6)°. Three intramolecular C—H⋯O, C—H⋯N and N—H⋯O hydrogen-bond interactions are present. The crystal structure is stabilized by two weak intermolecular C—H⋯O and C—H⋯N hydrogen-bond interactions.

Related literature

For the biological activity of 1-phenyl-3-methyl-4-benzoylpyrazolon-5-one and its metal complexes, see: Li et al. (1997 ▶); Liu et al. (1980 ▶); Zhou et al. (1999 ▶). For a related structure, see: Wang et al. (2003 ▶).

Experimental

Crystal data

C₂₅H₂₃N₃O₂
M _r = 397.46
Orthorhombic,
a = 17.685 (4) Å
b = 11.613 (2) Å
c = 20.568 (4) Å
V = 4224.1 (15) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.984, T _max = 0.990
32552 measured reflections
4852 independent reflections
4332 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.135
S = 1.12
4852 reflections
278 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.28 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 global, I. DOI: 10.1107/S1600536809040458/fl2271sup1.cif

e-65-o2740-sup1.cif^{(23KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809040458/fl2271Isup2.hkl

e-65-o2740-Isup2.hkl^{(237.8KB, 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—H3A⋯O1	0.96 (2)	1.86 (2)	2.6751 (17)	141.3 (18)
C2—H2⋯O1	0.95	2.28	2.8956 (19)	122
C6—H6⋯N1	0.95	2.49	2.812 (2)	100
C25—H25C⋯O1ⁱ	0.98	2.57	3.538 (2)	169
C24—H24⋯N1ⁱⁱ	0.95	2.61	3.551 (2)	174

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

Acknowledgments

The authors gratefully acknowledge the financial support of the National Natural Science Foundation of China (grant No. 20772066).

supplementary crystallographic information

Comment

1-Phenyl-3-methyl-4-benzoylpyrazolon-5-one (HPMBP), an effective β-diketonate, is widely used and well known for its extractive ability. In recent years, HPMBP and its metal complexes have also been found to have good antibacterial and biological properties. Its metal complexes have analgesic activity (Liu et al., 1980; Li et al., 1997; Zhou et al., 1999). In order to develop new medicines, we have synthesized the title compound, (I), and its structure is reported here.

The structure of (I) is shown in Fig. 1. The dihedral angles formed by the pyrazolone ring with the three benzene rings C1···C6, C12···C17 and C19···C24 are 14.59 (7), 79.35 (5) and 87.10 (6)°, respectively. The O atom of the 3-methyl-1-phenylpyrazol-5-one moiety and the N atom of the amino group are available for coordination with metals. The pyrazole ring is planar and atoms O1, C7, C8, C11 and N3 are almost coplanar fwith an rmsd value of 0.0093 and the largest deviation is 0.0144 (10) Å for atom C7. The dihedral angle between this mean plane and the pyrazoline ring of PMBP is 3.53 (7)°, close to the value of 3.56 (3)° found in 4-{[3,4-dihydro-5- methyl-3-oxo-2-phenyl-2H-pyrazol-4-ylidene(phenyl)methylamino}- 1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one(Wang et al., 2003). The bond lengths within this part of the molecule lie between classical single- and double-bond lengths, indicating extensive conjugation. A strong intramolecular N3—H3A···O1 hydrogen bond (Table 1) is observed, leading to a keto-enamine form. The molecule is further stabilized by a C—H···O weak intramolecular hydrogen bond (Table 1). The crystal structure also involves two weak intermolecular(C—H···O and C—H···N) hydrogen-bond interactions(Fig. 2).

Experimental

Compound (I) was synthesized by refluxing a mixture of 1-phenyl-3- methyl-4-benzoylpyrazol-5-one (10 mmol) and 4-methoxybenzylamine (10 mmol) in ethanol (80 ml) over a steam bath for about 4 h. Excess solvent was removed by evaporation and the solution was cooled to room temperature. After 2 days a yellow solid was obtained and this was dried in air. The product was recrystallized from ethanol, to afford yellow crystals of (I) suitable for X-ray analysis.