4-[(3-Hy­droxy­anil­ino)­(phenyl)­methyl­idene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Keraghel Saida; Benghanem Fatiha; Dehbi Ouarda; Ourari Ali; Ouari Kamel; Lydia Brelot

doi:10.1107/S1600536812023082

. 2012 May 26;68(Pt 6):o1909–o1910. doi: 10.1107/S1600536812023082

4-[(3-Hydroxyanilino)(phenyl)methylidene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Keraghel Saida ^a,^*, Benghanem Fatiha ^a, Dehbi Ouarda ^a, Ourari Ali ^a, Ouari Kamel ^a, Lydia Brelot ^b

PMCID: PMC3379466 PMID: 22719664

Abstract

In the title compound, C₂₃H₁₉N₃O₂, the dihedral angles formed by the pyrazolone ring with the three benzene rings are 30.91 (6), 60.96 (4) and 57.01 (4)°. The ligand is in the enamine–keto form and its structure is stabilized by an intramolecular N—H⋯O hydrogen bond. In the crystal, O—H⋯N hydrogen bonds link molecules into chains parallel to [01-1].

Related literature

For the synthesis and applications of pyrazolones and derivative compounds, see: Jensen (1959 ▶); Casas et al. (2007 ▶); Metwally et al. (1985 ▶); Morris et al. (1986 ▶); Raja et al. (2012 ▶); Delgado et al. (2006 ▶); Liskovskaya et al. (2006 ▶); Peng et al. (2004 ▶); Wang et al. (2002 ▶); Ramasamy et al. (2010 ▶); Thakar et al. (2010 ▶); Xu et al. (2006 ▶); Zhu et al. (2005 ▶); Wang et al. (2003 ▶).

Experimental

Crystal data

C₂₃H₁₉N₃O₂
M _r = 369.41
Triclinic,
a = 9.5239 (3) Å
b = 10.4564 (4) Å
c = 10.8120 (4) Å
α = 66.870 (1)°
β = 72.208 (1)°
γ = 72.908 (1)°
V = 924.04 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 K
0.18 × 0.18 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1995 ▶) T _min = 0.985, T _max = 0.990
11733 measured reflections
4227 independent reflections
3385 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.096
S = 1.05
4227 reflections
262 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812023082/vm2173sup1.cif

e-68-o1909-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023082/vm2173Isup2.hkl

e-68-o1909-Isup2.hkl^{(202.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812023082/vm2173Isup3.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
N1—H1N⋯O2	0.933 (16)	1.792 (17)	2.6189 (13)	146.1 (14)
O1—H1⋯N2ⁱ	0.93 (2)	1.84 (2)	2.7494 (13)	169.1 (18)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors would like to thank Professor Jean Claude Daran, Laboratoire de Chimie de Coordination, Toulouse, France, and Professor J. P. Gisselbrecht, Laboratoire d’Electrochimie et de Chimie Physique du Corps Solide, Strasbourg University, France, for their valuable contributions.

supplementary crystallographic information

Comment

4-Acyl-5-pyrazolones, a family of flexible β-diketonates and their derived Schiff bases are analgesics, antipyretics, anti-inflammatory agents and insecticides (Morris et al., 1986; Metwally et al., 1985; Casas et al., 2007; Raja et al., 2012). They have been widely used as extractants for metal traces (Delgado et al., 2006; Liskovskaya et al., 2006). Many of these compounds exhibit keto-enol tautomerism (Peng et al., 2004).

The reaction of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone with primary amines affords Schiff bases that can function as N– and O-donor tridentates ligands,(Wang et al., 2002; Ramasamy et al., 2010; Thakar et al., 2010; Xu et al., 2006; Zhu et al., 2005; Wang et al., 2003). In order to expand this field, a novel Schiff base has been synthesized and its crystal structure is reported herein for the first time. The compound (I) was prepared from the reaction of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (H1PMBP) and 3-aminophenol. The asymmetric unit of structure (I), and the atomic numbering used, are illustrated in Fig.1.

Steric hindrance affects this structure: the pyrazolone ring C14—N3 is not coplanar with the C18–C23 benzene ring and not perpendicular to the other two benzene rings C8–C13 and C1–C6. The dihedral angles are 30.92 (6), 60.96 (4) and 57.01 (4)°.

The O atom of the 3-methyl-1-phenylpyrazol-5-one unit and the N atom of the (3-hydroxyphenyl) amine group are available for coordination with metals. The pyrazolone ring is planar and atoms O2, C16, C14, C7 and N1 are coplanar, the largest deviation being 0.0179 (7) Å for atom C16. The dihedral angle between this plane (O2 C16 C14 C7 N1) and the pyrazolone ring of PMBP is 4.43 (8)°, close to the values of 4.01 (12)° found in (4Z)-[4 fluorobenzylamino)(phenyl)-methylene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one and 5.05 (3)° found in 4-[(2-hydroxyphenylamino)phenylmethylene] -5-methyl-2-phenyl-2H-pyrazol-3(4H)-one, respectively (Xu et al., 2006; Wang et al., 2002).

The C15—N2—N3—C18 torsion angle is 176.73 (10)° , different from the value of 16.7 (3)° in 3-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenylpyrazol-4-ylmino)-4,4,4-trifluoro-1-(2-thienyl)-butane-1,2-dione (Wang et al., 2002). Small torsion angles for N1 C7 C14 C16 [5.66 (17); O1 C1 C6 C5 [-178.76 (11)° ]and N1 C5 C6 C1 [-175.56 (11)° ] show that atoms O1, N1 and O2 are in a cis conformation and can act as the coordinating atoms of a tridentate ligand.

In the pyrazole ring, the bond lengths C14—C16, C14—C15, C15—N2, N2—N3 and C16—N3 lie between classical single and double bond lengths, indicating extensive conjugation and electron delocalization. The bond angles within this ring deviate by up to 4° from the 108° angle of a regular pentagon.

A strong intramolecular N1—H1N···O2 hydrogen bond (Table 1) is observed, leading to an enamine–keto tautomeric form. This case is similar to that found by Xu et al. (2006) for 4-[(2-hydroxyphenylamino)phenylmethylene] -5-methyl-2-phenyl-2H-pyrazol-3(4H)-one [N—O = 2.75 (3) Å and N3—H3···O1 = 143 (4)°]. The molecule is further stabilized by an intermolecular O—H···N hydrogen bond (Table1, Fig.2). Intermolecular O—H···N hydrogen bonds link molecules forming chains parallel to the [0 1 -1] direction. Part of the chain structure is shown in Fig.2.

Experimental

All reagents were obtained from commercial sources and used without further purification. H1PMBP was synthesized according to the method proposed by Jensen (Jensen,1959). Ethanol solution of 139 mg (0.1 mol) of H1PMBP and 54.5 mg (0.1 mol) of m-aminophenol were refluxed together for 24 h over a steam bath. The excess solvent was removed by evaporation. The title compound separated out as a yellow powder, which was collected, dried in air and dissolved afterwards in a hot mixture ethanol/water (9.5/0.5). A bright yellow single crystals, suitable for X-ray analysis, were obtained by slow cooling of a warmed ethanol solution for one night. The product is stable in air, and soluble in acetone and ethanol. Elemental analysis: calculated C 74.78, H 5.18, N 11.37%; found C 74.34, H 5.20, N 11.33%.