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

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

doi:10.1107/S1600536812006526

. 2012 Feb 24;68(Pt 3):o794. doi: 10.1107/S1600536812006526

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

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

PMCID: PMC3297862 PMID: 22412665

Abstract

A twist is evident in the title compound, C₂₁H₂₁N₃O₂, the dihedral angle between the terminal six-membered rings being 29.46 (10)°; the linked five- and six-membered rings are coplanar [1.30 (11)°]. The carbonyl O atom accepts intramolecular hydrogen bonds from the adjacent hydroxy and amine groups. The three-dimensional crystal packing is achieved through C—H⋯π interactions.

Related literature

For background to the synthesis, see: Gelin et al. (1983 ▶); Bendaas et al. (1999 ▶). For the structures of the 4-chloro and 4-methoxy analogues, see: Asiri, Al-Youbi, Alamry et al. (2011 ▶); Asiri, Al-Youbi, Faidallah et al. (2011 ▶).

Experimental

Crystal data

C₂₁H₂₁N₃O₂
M _r = 347.41
Monoclinic,
a = 14.9041 (8) Å
b = 6.9222 (4) Å
c = 17.1921 (8) Å
β = 96.190 (5)°
V = 1763.35 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.40 × 0.02 × 0.02 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.967, T _max = 0.998
12780 measured reflections
4055 independent reflections
2455 reflections with I > 2σ(I)
R _int = 0.076

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.164
S = 1.02
4055 reflections
246 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); 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/S1600536812006526/hg5179sup1.cif

e-68-0o794-sup1.cif^{(19.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812006526/hg5179Isup2.hkl

e-68-0o794-Isup2.hkl^{(198.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812006526/hg5179Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the C1–C6 and C15–C20 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.86 (1)	1.71 (2)	2.509 (2)	155 (4)
N3—H2⋯O2	0.89 (1)	1.91 (2)	2.671 (3)	143 (2)
C14—H14A⋯Cg1ⁱ	0.98	2.69	3.475 (2)	138
C14—H14C⋯Cg1ⁱⁱ	0.98	2.66	3.563 (2)	153
C17—H17⋯Cg2ⁱⁱⁱ	0.95	2.58	3.424 (2)	148

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

Acknowledgments

The authors are thankful to the Center of Excellence for Advanced Materials Research and the Chemistry Department of King Abdulaziz University for providing research facilities. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

supplementary crystallographic information

Comment

In connection with recent structural studies (Asiri, Al-Youbi, Alamry et al., 2011; (Asiri, Al-Youbi, Faidallah et al., 2011) of compounds prepared by reactions between pyrazoles and aniline derivatives following literature procedures (Gelin et al., 1983; Bendaas et al., 1999), the title compound, 3-(4-toluidino)-1-(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)but-2-en-1-one (I) was investigated.

While in (I), Fig. 1, the linked five- and six-membered rings are co-planar, forming a dihedral angle of 1.30 (11)°, there is a twist about the N3—C15 bond as seen in the value of the C13—N3—C15—C16 torsion angle of 146.9 (2)°; the dihedral angle between the terminal six-membered rings is 29.46 (10)°. The carbonyl-O2 atom accepts hydrogen bonds from the adjacent hydroxyl- and amine-groups, Table 1. These groups do not participate in intermolecular interactions. Rather, molecules are consolidated in the three-dimensional crystal packing by C—H···π interactions, Fig. 2 and Table 1.

Experimental

A solution of 4-acetoacetyl-5-hydroxy-3-methyl-1-phenylpyrazole (0.005 mol) and p-toluidine (0.005 mol) in ethanol (25 ml) was refluxed for 2 h. The precipitate, obtained from the hot solution, was collected, washed with methanol and recrystallized from its ethanol-benzene solution as yellow needles; M.pt: 419–421 K.