Crystal structure of (4E)-4-(8-meth­oxy-2H-chromen-2-yl­idene)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

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

doi:10.1107/S2056989015009445

. 2015 May 23;71(Pt 6):o414–o415. doi: 10.1107/S2056989015009445

Crystal structure of (4E)-4-(8-methoxy-2H-chromen-2-ylidene)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

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

PMCID: PMC4459315 PMID: 26090198

Abstract

In the title compound, C₂₀H₁₆N₂O₃, the phenyl substituent attached to the pyrazole ring makes a dihedral angle of 4.87 (7)° with the rest of the molecule. In the crystal, molecules are connected into inversion dimers of the R ₂ ²(14) type by pairs of C—H⋯O interactions. π–π interactions exist between the benzene and pyrazole rings at a distance of 3.701 (1) Å. Similarly, π–π interactions are present at a centroid–centroid distance of 3.601 (1) Å between the oxygen-containing heterocyclic ring and methoxy substituted aromatic ring of a neighbouring molecule. Additional C—H⋯π and C=O⋯π interactions are also observed.

Keywords: crystal structure, pyrazolone, 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-71-0o414-scheme1.jpg

Experimental

Crystal data

C₂₀H₁₆N₂O₃
M _r = 332.35
Monoclinic,
a = 28.179 (5) Å
b = 4.7108 (8) Å
c = 23.819 (5) Å
β = 92.957 (7)°
V = 3157.7 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.40 × 0.22 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▸) T _min = 0.961, T _max = 0.985
13056 measured reflections
3419 independent reflections
2389 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.127
S = 1.06
3419 reflections
229 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.16 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/S2056989015009445/im2465sup1.cif

e-71-0o414-sup1.cif^{(26.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015009445/im2465Isup2.hkl

e-71-0o414-Isup2.hkl^{(187.8KB, hkl)}

Click here for additional data file.^{(6.7KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015009445/im2465Isup3.cml

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

. DOI: 10.1107/S2056989015009445/im2465fig1.tif

View of the title compound with the atom numbering scheme. Thermal ellipsoids are drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radii.

Click here for additional data file.^{(1.9MB, tif)}

PLATON . DOI: 10.1107/S2056989015009445/im2465fig2.tif

Partial packing (PLATON; Spek, 2009) which shows that molecules are dimerized due to C—H⋯O bondings.

CCDC reference: 1401584

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

Table 1. Hydrogen-bond geometry and CH and CO interactions (, ).

Cg1 and Cg2 are the centroids of the N1/N2/C7C9 and C11C14/C19/O2 rings, respectively.

DHA	DH	HA	D A	DHA
C6H6O1	0.93	2.28	2.911(2)	124
C12H12O1	0.93	2.38	3.004(2)	124
C13H13O1ⁱ	0.93	2.53	3.2577(19)	136
C10H10A Cg1ⁱⁱ	0.96	2.79	3.6812(17)	155
C7O1Cg2ⁱⁱⁱ	1.23(1)	3.65(1)	3.9797(18)	96(1)

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

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). No crystal structure has been found containing a 8-methoxy-2H-chromene subunit. (I) is synthesized for the biological studies etc.

In (I), the benzene ring A (C1–C6) and the (4E)-4-(8-methoxy-2H-chromen-2-ylidene)-5-methyl-2,4-dihydro-3H-pyrazol-3-one (C7 –C20/N1/N2/O1/O2/O3) part of the molecule are planar with r. m. s. deviations of 0.0053 and 0.0108 Å, respectively. The dihedral angle between A/B is 4.87 (7)°. The molecules are dimerized due to C—H···O interactions completing R₂² (14) Molecules are connected to inversion dimers dimerized of the R₂² (14) type by C—H···O interactions. There exist π–π interactions at a distance of 3.7011 (12) Å between the centeroids of Cg1—Cg3ⁱ and Cg3—Cg1ⁱⁱ [i = x, - 1 + y, z and ii = x, 1 + y, z], where Cg1 and Cg3 are the centroids of heterocyclic ring C (N1/N2/C7/C8/C9) and benzene ring A, respectively. Similarly, there exist π–π interaction at a distance of 3.6012 (11) Å between the centeroids of Cg2—Cg4ⁱⁱ and Cg4—Cg2ⁱ [i = x, - 1 + y, z and ii = x, 1 + y, z], where Cg2 and Cg4 are the centroids of heterocyclic ring D (C11—C14/C19/O2) and methoxy containing benzene ring E (C14—C19), respectively. There exist C—H···π and C=O···π interactions (Table 1).

S2. Experimental

For the preparation of title compound (I), a mixture of 4-acetyl-3-methyl-1-phenyl-5-hydroxy pyrazole (0.218 g, 1 mmoL), 2-methoxybenzaldehyde (0.205 g, 1.5 mmoL) was refluxed for 8 h in glacial acetic acid (15 ml) and concentrated sulfuric acid (0.2 ml). The reaction mixture was diluted with distilled water (60 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 needles (yield = 63%, m.p. 503 K)