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

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

doi:10.1107/S1600536811032491

. 2011 Aug 17;67(Pt 9):o2353. doi: 10.1107/S1600536811032491

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

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

PMCID: PMC3200693 PMID: 22064834

Abstract

The central residue in the title compound, C₂₁H₂₁N₃O₃, is close to planar (r.m.s. deviation = 0.0753 Å for all non-H atoms from OH to NH inclusive): the hydroxy, amino and carbonyl groups all lie to the same side of the molecule (the conformation about the ethene bond is Z), facilitating the formation of intramolecular O—H⋯O and N—H⋯O hydrogen bonds that close S(6) rings. However, overall the molecule is twisted as the terminal aromatic rings are not coplanar with the central plane [dihedral angles = 20.55 (5) and 80.90 (4)° for the N-bound phenyl ring and the methoxybenzene ring, respectively]. The dihedral angle between the rings is 82.14 (7)°. Supramolecular layers in the ac plane mediated by C—H⋯π interactions are found in the crystal.

Related literature

For background to the synthesis, see: Gelin et al. (1983 ▶); Bendaas et al. (1999 ▶). For the structure of the 4-chloro derivative, see: Asiri et al. (2011 ▶).

Experimental

Crystal data

C₂₁H₂₁N₃O₃
M _r = 363.41
Monoclinic,
a = 9.5717 (3) Å
b = 16.9516 (6) Å
c = 11.3143 (4) Å
β = 104.946 (4)°
V = 1773.70 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.09 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 = 0.837, T _max = 1.000
8486 measured reflections
3939 independent reflections
3145 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.104
S = 1.05
3939 reflections
255 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.23 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/S1600536811032491/hb6355sup1.cif

e-67-o2353-sup1.cif^{(21.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811032491/hb6355Isup2.hkl

e-67-o2353-Isup2.hkl^{(193.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811032491/hb6355Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the N1,N2,C1–C3 and C15–C20 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.86 (1)	1.68 (1)	2.4963 (15)	156 (2)
N3—H3⋯O2	0.89 (1)	1.92 (1)	2.6447 (16)	138 (2)
C14—H14b⋯Cg1ⁱ	0.98	2.88	3.5542 (18)	127
C21—H21c⋯Cg2ⁱⁱ	0.98	2.76	3.5195 (17)	134

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

Acknowledgments

The authors are thankful to the Center of Excellence for Advanced Materials Research and the Chemistry Department at King Abdulaziz University for providing research facilities. Dr Al-Amry is thanked for support. The authors also thank the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

In connection with a recent structural study (Asiri et al., 2011), the title compound (I) was prepared as a part of on-going investigations of reactions between pyrazoles and aniline derivatives (Gelin et al., 1983; Bendaas et al., 1999).

The molecular structure of (I), Fig. 1, resembles closely that of the 4-chloroanilino derivative (Asiri et al., 2011) and features a Z configuration about the C12—C13 [1.381 (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 direct consequence of this is that the central residue is planar; the values of the C1—C2—C11—O2, C2—C11—C12—C13 and C11—C12—C13—N3 torsion angles are -3.6 (2), -171.74 (15) and -1.7 (2) °, respectively. The benzene and 4-methoxybenzene rings are each twisted out of the central plane as seen in the values of the C1—N1—C5—C6 and C13—N3—C15—C16 torsion angles of 159.97 (15) and -74.5 (2) °, respectively.

The most prominent feature of the crystal packing is the formation of supramolecular layers in the ac plane and mediated by C—H···π interactions, Fig. 2. and Table 1. Layers stack along the b axis as shown in Fig. 3.

Experimental

A solution of 4-acetoacetyl-5-hydroxy-3-methyl-1-p-sulfamylphenypyrazole (1.7 g, 0.005 mole) and 4-methoxyaniline (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 yellow blocks; M.pt: 507–507 K.