(4Z)-4-[(2E)-1-Hy­droxy-3-(3-nitro­phen­yl)prop-2-en-1-yl­idene]-3-methyl-1-(4-methyl­phen­yl)-1H-pyrazol-5(4H)-one

Faryal Chaudhry; M Nawaz Tahir; Misbahul Ain Khan; Abdul Qayyum Ather; Nadia Asif

doi:10.1107/S1600536812025238

. 2012 Jun 13;68(Pt 7):o2044. doi: 10.1107/S1600536812025238

(4Z)-4-[(2E)-1-Hydroxy-3-(3-nitrophenyl)prop-2-en-1-ylidene]-3-methyl-1-(4-methylphenyl)-1H-pyrazol-5(4H)-one

Faryal Chaudhry ^a, M Nawaz Tahir ^b,^*, Misbahul Ain Khan ^c, Abdul Qayyum Ather ^d, Nadia Asif ^a

PMCID: PMC3393312 PMID: 22807869

Abstract

In the title compound, C₂₀H₁₇N₃O₄, the dihedral angles between the heterocyclic ring and the toluene and nitrobenzene rings are 4.21 (15) and 11.43 (14)°, respectively. The whole molecule is close to planar (r.m.s. deviation for the 27 non-H atoms = 0.171 Å). Two S(6) rings are formed due to intramolecular C—H⋯O and O—H⋯O hydrogen bonds. In the crystal, inversion dimers linked by pairs of C—H⋯O bonds generate R ₂ ²(10) loops and further C—H⋯O bonds link the dimers along the b-axis direction. There exist π–π interactions between the heterocyclic rings at a centroid–centroid distance of 3.7126 (10) Å and between the centroids of the benzene rings at a distance of 3.8710 (16) Å.

Related literature

For background and a related structure, see: Mukhtar et al. (2010 ▶). For other related structures, see: Udaya Lakshmi et al. (2005 ▶); Jadeja & Shah (2007 ▶).

Experimental

Crystal data

C₂₀H₁₇N₃O₄
M _r = 363.37
Monoclinic,
a = 19.8712 (16) Å
b = 12.1917 (10) Å
c = 16.733 (2) Å
β = 121.188 (4)°
V = 3467.9 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.35 × 0.18 × 0.17 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.972, T _max = 0.983
12231 measured reflections
3328 independent reflections
1823 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.143
S = 1.02
3328 reflections
247 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812025238/hb6835sup1.cif

e-68-o2044-sup1.cif^{(25.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025238/hb6835Isup2.hkl

e-68-o2044-Isup2.hkl^{(160KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812025238/hb6835Isup3.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1	0.82	1.82	2.571 (3)	152
C6—H6⋯O1	0.93	2.33	2.958 (3)	125
C18—H18⋯O4ⁱ	0.93	2.57	3.496 (3)	171
C20—H20⋯O3ⁱⁱ	0.93	2.43	3.172 (3)	136

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

Acknowledgments

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

supplementary crystallographic information

Comment

We have reported the synthesis and crystal structure of (II) i.e., Ethyl 2-benzamido-4,5,6,7-tetrahydro-1-benzothiophene-3-carboxylate (Mukhtar et al., 2010). The title compound (I, Fig. 1) is being reported here in continuation to synthesize various thiophene derivatives.

The crystal structure of 3-nitrocinnamic acid (Udaya Lakshmi et al., 2005) and 5-methyl-4-(phenyl(phenylamino)methylene)-2-p-tolyl-2,4-dihydropyrazol-3-one (Jadeja & Shah, 2007) have been published which contain the fragments of the title compound.

In (I), the toluene group A (C1—C7) and the part of 5-methyl-2,4-dihydro- 3H-pyrazol-3-one B (C8—C11/N1/N2/O1) are planar with r.m.s. deviation of 0.0052 and 0.0171 Å, respectively. The dihedral angle between A/B is 4.42 (10)°. The part of 3-nitrocinnamic acid C (C12—C20/N3/O2/O3/O4) has r. m. s. deviation of 0.1229 Å from the plane in which O3 atom deviate to 0.2632 (17) Å. The dihedral angle between A/C abd B/C is 7.93 (6) and 12.26 (7)°, respectively. In the title compound two S(6) ring motifs are formed due to intramolecular H-bondings of C—H···O and O—H···O types (Table 1, Fig. 1). The molecules are dimerized from nitrobenzene due to C—H···O type of H-bondings and form R₂²(10) ring motifs (Table 1, Fig. 2). The dimers are again interlinked from nitrobenzene due to C—H···O type of H-bondings. There exist π···π interaction between Cg1···Cg1ⁱ [i = - x, y, 1/2 - z] at a distance of 3.7126 (10) Å, where Cg1 is the centroid of heterocyclic five membered ring (N1/N2/C8/C10/C11). Similarly, there also exist π···π interaction between Cg2···Cg3ⁱⁱ [ii = - x, - y, 1 - z] and Cg3···Cg2ⁱⁱ at a distance of 3.8710 (16) Å, where Cg2 and Cg3 are the centroids of benzene rings (C1—C6) and (C15—C20).

Experimental

1-(5-Hydroxy-3-methyl-1-p-tolyl-1H-pyrazol-4-yl)ethanone (1 g, 4.34 mmol), m-nitrobenzaldehyde (0.65 g; 4.34 mmol), with one drop of piperidine in ethanol (30 ml) was heated on boiling water bath for half an hour and crude product was obtained on cooling. The product was recrystallized by ethanol to get orange needles of the title compound.