Ethyl 6-(4-meth­oxy­phen­yl)-2-oxo-4-phenyl­cyclo­hex-3-ene­carboxyl­ate

Hoong-Kun Fun; Abbas Farhadikoutenaei; B K Sarojini; B J Mohan; B Narayana

doi:10.1107/S1600536812036446

. 2012 Aug 25;68(Pt 9):o2788–o2789. doi: 10.1107/S1600536812036446

Ethyl 6-(4-methoxyphenyl)-2-oxo-4-phenylcyclohex-3-enecarboxylate

Hoong-Kun Fun ^a,^*, Abbas Farhadikoutenaei ^a,^‡, B K Sarojini ^b, B J Mohan ^b, B Narayana ^c

PMCID: PMC3435819 PMID: 22969665

Abstract

The asymmetric unit of the title compound, C₂₂H₂₂O₄, consists of two independent molecules (A and B). The cyclohexene rings adopt slightly distorted sofa conformations in both molecules. The dihedral angles between the benzene rings are 74.16 (13) and 71.85 (13)° in molecules A and B, respectively. In the crystal, weak C—H⋯O hydrogen bonds link the molecules into a ribbon-like structure along the b axis. Weak C—H⋯π interactions are also observed.

Related literature

For applications of chalcones and cyclohexenone derivatives, see: Padmavathi et al. (2000 ▶); Senguttuvan & Nagarajan (2010 ▶); Tanaka et al. (1997 ▶). For related structures, see: Dutkiewicz et al. (2011a ▶,b ▶,c ▶); Fun et al. (2008 ▶); Fischer et al. (2008 ▶). For conformation analysis, see: Cremer & Pople (1975 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₂H₂₂O₄
M _r = 350.40
Orthorhombic,
a = 22.3528 (13) Å
b = 8.1659 (5) Å
c = 19.7132 (12) Å
V = 3598.3 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.37 × 0.24 × 0.17 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.968, T _max = 0.985
35140 measured reflections
5622 independent reflections
4938 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.139
S = 1.08
5622 reflections
473 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) globl, I. DOI: 10.1107/S1600536812036446/lh5518sup1.cif

e-68-o2788-sup1.cif^{(44.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036446/lh5518Isup2.hkl

e-68-o2788-Isup2.hkl^{(275.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812036446/lh5518Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the C13A–C18A and C13B–C18B rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5A—H5AA⋯O1A ⁱ	0.95	2.41	3.210 (3)	141
C5B—H5BA⋯O1B ⁱ	0.95	2.53	3.329 (3)	142
C14B—H14B⋯O2A	0.95	2.43	3.377 (3)	173
C17A—H17A⋯O2B ⁱ	0.95	2.59	3.218 (4)	124
C21A—H21A⋯Cg1ⁱ	0.99	2.70	3.513 (3)	142
C21B—H21D⋯Cg2ⁱ	0.99	2.71	3.501 (3)	139

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

HKF and AFK thank Universiti Sains Malaysia (USM) for the Research University Grant No. 1001/PFIZIK/811160. BKS gratefully acknowledges the Department of Atomic Energy (DAE)/BRNS, Government of India, for providing financial assistance for the BRNS project (No. 2011/34/20-BRNS/0846).

supplementary crystallographic information

Comment

Chalcones undergo a variety of chemical reactions and were found to be useful in the synthesis of various heterocyclic compounds. Michael addition of ethyl acetoacetate to chalcones yield 4,6-diaryl-2-oxo-cyclohex-3-ene-1-carboxylate derivatives, which could be used for the synthesis of fused heterocycles like isoxazoles, pyrazoles and quinazolins (Padmavathi et al., 2000; Senguttuvan & Nagarajan, 2010). Cyclohexenone derivatives are well known lead molecules for the treatment of inflammation and autoimmune diseases (Tanaka et al., 1997). The crystal structure of some of the cyclohexenone derivatives have been reported (Dutkiewicz et al., 2011a,b,c; Fun et al., 2008; Fischer et al., 2008). The present work describes the synthesis and crystal structure of the title compound which was prepared by the reaction of 1-phenyl-3-(4-methoxyphenyl)- prop-2-en-1-one with ethyl acetoacetate.

The asymmetric unit of the title compound, (Fig 1), consists of two independent molecules (A and B). The cyclohexene rings (C7A–C12A and C7B–C12B) adopt slightly distorted sofa conformations with puckering parameters (Cremer & Pople, 1975) Q = 0.495 (3) Å, Θ = 126.1 (3) Å, φ = 316.5 (4)° and Q = 0.491 (3) Å, Θ = 54.2 (3) Å, φ = 129.5 (4)°, respectively. The dihedral angle between the benzene rings (C1–C6 and C13–C18) are 74.16 (13)° in molecule A and 71.85 (13) ° in molecule B. In the crystal (Fig 2), intermolecular C—H···O hydrogen bonds link the molecules into a ribbon-like structure along the b axis. The crystal structure is further stabilized by weak C—H···π interactions (Table 1), involving the C13A–C18A ring (centroid Cg1) and C13B–C18B ring (centroid Cg2).

Experimental

1-Phenyl-3-(4-methoxyphenyl)-prop-2-en-1-one (2.38 g, 0.01 mol) and ethyl acetoacetate (1.30 g, 0.01 mol) were refluxed for 8–10 hrs in 30 ml methanol in presence of 0.8 ml of 10% NaOH. The reaction mixture was cooled to room temperature and the precipitate obtained was filtered. The single crystals were grown by slow evaporation from solvent ethanol. M.P = 375–377 K