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

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

doi:10.1107/S205698901500883X

. 2015 May 13;71(Pt 6):o393–o394. doi: 10.1107/S205698901500883X

Crystal structure of (4Z)-4-[(2E)-3-(4-chlorophenyl)-1-hydroxyprop-2-en-1-ylidene]-5-methyl-2-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: PMC4459345 PMID: 26090184

Abstract

In the the asymmetric unit of the title compound, C₁₉H₁₅ClN₂O₂, there are two symmetry-independent molecules, which adopt similar conformations. The largest difference is observed in the dihedral angles between the phenyl and the pyrazole fragments [17.00 (12) and 23.42 (10)°]. A strong intramolecular O—H⋯O hydrogen bond with the S (6) motif is observed in both molecules. Pairs of π–π stacking interactions between the phenyl groups [centroid–centroid distances = 3.6627 (13) and 3.7156 (14) Å] assemble the molecules into two types of centrosymmetric dimers. Weak C—H⋯O interactions connect molecules into chains along the b axis.

Keywords: crystal structure, intramolecular O—H⋯O hydrogen bond, C—H⋯O interactions, π–π stacking interactions

Related literature

For related structures and background, see: Chaudhry et al. (2012 ▸); Holzer et al. (1999 ▸); Malik et al. (2009 ▸). graphic file with name e-71-0o393-scheme1.jpg

Experimental

Crystal data

C₁₉H₁₅ClN₂O₂
M _r = 338.78
Triclinic,
a = 11.3207 (6) Å
b = 11.4044 (6) Å
c = 15.2839 (9) Å
α = 70.567 (3)°
β = 70.925 (3)°
γ = 62.621 (2)°
V = 1616.40 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 296 K
0.35 × 0.28 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▸) T _min = 0.919, T _max = 0.963
24363 measured reflections
6925 independent reflections
4587 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.155
S = 1.02
6925 reflections
437 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.32 e Å⁻³

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/S205698901500883X/gk2632sup1.cif

e-71-0o393-sup1.cif^{(38.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500883X/gk2632Isup2.hkl

e-71-0o393-Isup2.hkl^{(379.4KB, hkl)}

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S205698901500883X/gk2632fig1.tif

View of the asymmetric unit. The displacement ellipsoids are drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radii.

Click here for additional data file.^{(1.2MB, tif)}

PLATON . DOI: 10.1107/S205698901500883X/gk2632fig2.tif

The partial packing (PLATON; Spek, 2009) showing fragments of two chains via C—H⋯O interactions.

CCDC reference: 1063448

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O2H2AO1	0.82	1.78	2.542(2)	153
C16H16O1ⁱ	0.93	2.47	3.239(2)	140
O4H4AO3	0.82	1.78	2.540(2)	153
C37H37O3ⁱⁱ	0.93	2.61	3.314(3)	133

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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). The title compound was synthesized for the biological studies as well as for the preparation of different metal complexes.

There are two symmetry independent molecules in the asymmetric unit. In one molecule, the benzene ring A (C1—C6), the 5-methyl-2,4-dihydro -3H-pyrazol-3-one moiety B (C7–C10/N1/N2/O1), prop-2-en-1-ol group C (C11/C12/C13/O2) and chlorobenzene group D (C14—C19/CL1) are planar with r. m. s. deviations of 0.0062, 0.0131, 0.0319 and 0.0050 Å, respectively. The dihedral angle between A/B, B/C, C/D and A/D is 23.21 (9), 6.20 (10), 18.48 (12) and 1.15 (12)°, respectively. In the second molecule, similar groups i.e. the benzene ring E (C20—C25), the 5-methyl-2,4- dihydro-3H-pyrazol-3-one moiety F (C26–C29/N3/N4/O3), prop-2-en-1-ol group G (C30/C31/C32/O4) and chlorobenzene group H (C33—C38/CL2) are planar with r. m. s. deviations of 0.0041, 0.0080, 0.0272 and 0.0144 Å, respectively. The dihedral angle between E/F, F/G, G/H and E/H is 16.74 (10), 5.66 (12), 13.81 (13) and 3.07 (13)°, respectively. There exist strong intramolecular hydrogen bond O—H····O (Table 1, Fig. 1) forming S(6) ring motif (Bernstein et al., 1995) in each molecule. The molecules are interlinked with each other due to C—H···O interactions (Table 1, Fig. 2). There exist π–π interactions with a distance of 3.6627 (13) Å between the centeroids of Cg2—Cg3ⁱ and Cg3—Cg2ⁱ [i = -x, -y, 1 - z], where Cg2 and Cg3 are the centroids of the benzene ring A (C1—C6) and the benzene ring D (C14–C19), respectively. Similarly, there exist π–π interactions with a distance of 3.7156 (14) Å between the centeroids of Cg5—Cg6ⁱⁱ and Cg6—Cg5ⁱⁱ [ii = 2 - x, -y, 1 - z], where Cg5 and Cg6 are the centroids of the benzene ring E (C20—C25) and the benzene ring H (C33–C38), respectively.

S2. Experimental

For the preparation of title compound, 4-acetyl-3-methyl-1-phenyl-5-hydroxy pyrazole (0.218 g, 1 mmoL), 4-chlorobenzaldehyde (0.211 g, 1.5 mmoL) in glacial acetic acid (10 ml) and concentrated sulfuric acid (0.2 ml) were stirred at 353–360 K for 5 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 using n-hexane to afford red plates (yield 53%; m.p. 483 K).