Crystal structure of (4Z)-4-[(2E)-3-(2-chloro­phen­yl)-1-hy­droxy­prop-2-en-1-yl­idene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Muhammad Shahid; Munawar Ali Munawar; Muhammad Nawaz Tahir; Muhammad Salim; Khizar Iqbal Malik

doi:10.1107/S2056989015009020

. 2015 May 20;71(Pt 6):o407–o408. doi: 10.1107/S2056989015009020

Crystal structure of (4Z)-4-[(2E)-3-(2-chlorophenyl)-1-hydroxyprop-2-en-1-ylidene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Muhammad Shahid ^a, Munawar Ali Munawar ^a, Muhammad Nawaz Tahir ^b,^*, Muhammad Salim ^a, Khizar Iqbal Malik ^a

PMCID: PMC4459312 PMID: 26090193

Abstract

In the title compound, C₁₉H₁₅ClN₂O₂, the pyrazole ring is almost planar (r.m.s. deviation = 0.002 Å) and subtends dihedral angles of 5.31 (16) and 1.86 (16)° with the phenyl and chlorobenzene rings, respectively. An intramolecular O—H⋯O hydrogen bond closes an S(6) ring and a short C—H⋯O contact is also observed. In the crystal, molecules are linked by weak C—H⋯O interactions to generate (001) sheets. Weak aromatic π–π interactions between the chlorobenzene and pyrazole rings, with a centroid–centroid distance of 3.7956 (17) Å are also observed.

Keywords: crystal structure, pyrazole, hydrogen bonding, π–π interactions

Related literature

For related structures, see: Chaudhry et al. (2012 ▸); Holzer et al. (1999 ▸); Malik et al. (2009 ▸). graphic file with name e-71-0o407-scheme1.jpg

Experimental

Crystal data

C₁₉H₁₅ClN₂O₂
M _r = 338.78
Orthorhombic,
a = 7.2348 (3) Å
b = 12.8737 (6) Å
c = 17.7843 (7) Å
V = 1656.41 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 296 K
0.34 × 0.28 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▸) T _min = 0.923, T _max = 0.960
8199 measured reflections
3593 independent reflections
2455 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.091
S = 1.00
3593 reflections
219 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack x determined using 771 quotients [(I ⁺)−(I ⁻)]/[(I ⁺)+(I ⁻)] (Parsons et al., 2013 ▸)
Absolute structure parameter: −0.06 (4)

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸) and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015009020/hb7419sup1.cif

e-71-0o407-sup1.cif^{(25.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015009020/hb7419Isup2.hkl

e-71-0o407-Isup2.hkl^{(197.3KB, hkl)}

Click here for additional data file.^{(6.3KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015009020/hb7419Isup3.cml

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S2056989015009020/hb7419fig1.tif

View of the title compound with displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S2056989015009020/hb7419fig2.tif

The partial packing, which shows that molecules are interlinked due to O—H⋯O bondings.

CCDC reference: 1400008

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O2H2AO1	0.82	1.74	2.501(3)	154
C6H6O1	0.93	2.29	2.933(4)	126
C10H10BO2ⁱ	0.96	2.55	3.444(4)	155
C16H16O2ⁱⁱ	0.93	2.56	3.405(4)	151

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

Acknowledgments

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan.

supplementary crystallographic information

S1. Comment

The crystal structures of 5-methyl-2-phenyl-4-((E)-3-phenyl-2-hydroxy- prop-2-enylidene)-1,2-dihydro-3H-pyrazol-3-one (Holzer et al., 1999), (4Z)-4-((2E)-1-hydroxy-3-(4-methoxyphenyl)prop-2-en-1- ylidene)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one (Malik et al., 2009) and (4Z)-4-((2E)-1-hydroxy-3-(3-nitrophenyl)prop- 2-en-1-ylidene)-3-methyl-1-(4-methylphenyl)-1H-pyrazol-5(4H)-one (Chaudhry, et al., 2012) have been published which are related to the title compound (I, Fig. 1). (I) is synthesized for the biological studies as well as for the preparation of different metal complexes.

In (I), the benzene ring A (C1–C6) and the 4-[(2E)-3-(2-chlorophenyl)-1- hydroxyprop-2-en-1-ylidene]-5-methyl-2,4-dihydro-3H-pyrazol-3-one moiety (C7 –C19/N1/N2/O1/O2/CL1) are planar with r. m. s. deviation of 0.0016 and 0.0158 Å, respectively. The dihedral angle between A/B is 4.87 (14)°. There exist intramolecular H-bonding of O—H···O type completing S (6) loop (Bernstein et al., 1995). The molecules are interlimked due to C—H···O interactions (Table 1, Fig. 2). There exist π–π interactions at a distance of 3.7956 (17) Å between the centeroids of Cg1—Cg2ⁱ and Cg2— Cg1ⁱⁱ [i = 1 + x, y, z and ii = -1 + x, y, z], where Cg1 and Cg2 are the centroids of heterocyclic ring C (N1/N2/C7/C8/C9) and chloro containing benzene ring D (C14–C19), respectively.

S2. Experimental

4-Acetyl-3-methyl-1-phenyl-5-hydroxypyrazole (0.218 g, 1 mmol), 2-chlorobenzaldehyde (0.211 g, 1.5 mmol) in glacial acetic acid (10 ml) and concentrated sulfuric acid (0.2 ml) was stirred at 353–360 K for 6 h. The reaction mixture was diluted with distilled water (50 ml). The precipitate was filtered, washed with methanol and dried. The crude product was purified by column chromatography using n-hexane and ethyl acetate mixtures as eluents. The product was recrystallized from n-hexane solution to afford yellow plates. Yield = 60%; m.p. 453 K