(2Z)-3-(4-Chloro­anilino)-1-(5-hy­droxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)but-2-en-1-one

Abdullah M Asiri; Abdulrahman O Al-Youbi; Khalid A Alamry; Hassan M Faidallah; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536811029473

. 2011 Jul 30;67(Pt 8):o2157. doi: 10.1107/S1600536811029473

(2Z)-3-(4-Chloroanilino)-1-(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)but-2-en-1-one

Abdullah M Asiri ^a,^b,^‡, Abdulrahman O Al-Youbi ^a, Khalid A Alamry ^a, Hassan M Faidallah ^a, Seik Weng Ng ^c,^a, Edward R T Tiekink ^c,^*

PMCID: PMC3213593 PMID: 22091170

Abstract

With the exception of the terminal benzene rings, the atoms in the title compound, C₂₀H₁₈ClN₃O₂, are approximately coplanar (r.m.s. deviation = 0.0495 Å). The benzene/chlorobenzene rings form dihedral angles of 3.02 (4) and 41.59 (5)°, respectively, with this plane. The hydroxy, amino and carbonyl groups all lie to the same side of the molecule, enabling the formation of intramolecular O—H⋯O and N—H⋯O hydrogen bonds that close S(6) rings. The configuration about the 2-butene bond is Z. Supramolecular chains mediated by C—H⋯Cl interactions and aligned along the c axis are found in the crystal packing. These assemble into layers that are connected by weak π–π interactions between centrosymmetrically related chlorobenzene rings [3.8156 (9) Å].

Related literature

For background to the synthesis, see: Gelin et al. (1983 ▶); Bendaas et al. (1999 ▶).

Experimental

Crystal data

C₂₀H₁₈ClN₃O₂
M _r = 367.82
Monoclinic,
a = 10.7782 (3) Å
b = 12.6349 (4) Å
c = 12.9071 (4) Å
β = 100.956 (3)°
V = 1725.67 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.931, T _max = 0.953
8785 measured reflections
3860 independent reflections
3199 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.103
S = 1.01
3860 reflections
245 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811029473/hg5069sup1.cif

e-67-o2157-sup1.cif^{(20.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811029473/hg5069Isup2.hkl

e-67-o2157-Isup2.hkl^{(189.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811029473/hg5069Isup3.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
O1—H1⋯O2	0.96 (3)	1.64 (3)	2.5283 (16)	153 (3)
N3—H3⋯O2	0.91 (2)	1.93 (2)	2.6678 (18)	136.9 (18)
C4—H4⋯Cl1ⁱ	0.95	2.81	3.6217 (18)	144

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are thankful to the Center of Excellence for Advanced Materials Research and the Chemistry Department at King Abdulaziz University for providing the research facilities. They also thank the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

The title compound (I) was isolated during an investigation of reactions between pyrazoles and aniline derivatives following literature precedents (Gelin et al., 1983; Bendaas et al., 1999). The molecular structure of (I), Fig. 1, features a Z configuration about the C12—C13 [1.376 (2) Å] bond. The hydroxy and amino groups are syn to the central carbonyl group and each forms a hydrogen bond to close a S(6) ring (Table 1). A result of this feature of the structure is that the central residue is planar; the values of the C10—C9—C11–O2, C9—C11—C12—C13 and C11—C12—C13—N3 torsion angles are 2.5 (2), -177.93 (14) and -0.4 (2) °, respectively. Indeed, the r.m.s. deviation for the non-hydrogen atoms comprising the entire molecule excluding the terminal benzene rings is 0.0495 Å. The benzene and chlorobenzene rings form dihedral angles of 3.02 (4) and 41.59 (5) °, respectively, with the central plane.

The most prominent feature of the crystal packing is the formation of supramolecular chains mediated by C—H···Cl interactions, Table 1. The chains assemble into layers in the bc plane, Fig. 2. The closest interactions between layers stacking along the a direction are weak π–π contacts between centrosymmetrically related chlorobenzene rings [3.8156 (9) Å for symmetry operation: 2 - x, 1 - y, 2 - z].

Experimental

A solution of 4-acetoacetyl-5-hydroxy-3-methyl-1-p-sulfamylphenypyrazole (1.7 g, 0.005 mol) and 4-chloroaniline (0.63 g, 0.005 mole) in ethanol (25 ml) was refluxed for 2 h. The precipitate, obtained from the hot solution, was collected, washed with methanol, and recrystallized from ethanol-benzene as orange crystals; M.pt 505–507 K.