Crystal structure of ethyl (E)-4-(4-chlorophen­yl)-4-meth­oxy-2-oxobut-3-enoate

Darlene Correia Flores; Juliano Rosa de Menezes Vicenti; Bruna Ávila Pereira; Gabriele Marques Dias da Silva; Priscilla Jussiane Zambiazi

doi:10.1107/S1600536814017280

. 2014 Aug 16;70(Pt 9):o1025. doi: 10.1107/S1600536814017280

Crystal structure of ethyl (E)-4-(4-chlorophenyl)-4-methoxy-2-oxobut-3-enoate

Darlene Correia Flores ^a,^*, Juliano Rosa de Menezes Vicenti ^a, Bruna Ávila Pereira ^a, Gabriele Marques Dias da Silva ^a, Priscilla Jussiane Zambiazi ^b

PMCID: PMC4186072 PMID: 25309205

Abstract

In the title compound, C₁₃H₁₃ClO₄, the dihedral angle between the chlorobenezene ring and the least-squares plane through the 4-methoxy-2-oxobut-3-enoate ethyl ester residue (r.m.s. deviation = 0.0975 Å) is 54.10 (5)°. In the crystal, molecules are connected by methoxy–ketone and benzene–carboxylate carbonyl C—H⋯O interactions, generating a supramolecular layer in the ac plane.

Keywords: crystal structure, methoxy–ketone interactions, benzene–carboxylate carbonyl interactions, 4-methoxy-2-oxobut-3-enoate ethyl ester

Related literature

For background to 1,2,4-trielectrophile systems, see: Machado et al. (2007 ▶); Siddiqui et al. (2013 ▶). For C—H⋯O interactions, see: Thakur et al. (2010 ▶).

Experimental

Crystal data

C₁₃H₁₃ClO₄
M _r = 268.68
Monoclinic,
a = 9.4557 (4) Å
b = 16.6411 (7) Å
c = 8.4319 (3) Å
β = 105.644 (2)°
V = 1277.64 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 K
0.76 × 0.67 × 0.59 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: gaussian (XPREP; Bruker, 2009 ▶) T _min = 0.667, T _max = 0.746
30885 measured reflections
3130 independent reflections
2613 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.135
S = 1.07
3130 reflections
167 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 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: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814017280/tk5332sup1.cif

e-70-o1025-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814017280/tk5332Isup2.hkl

e-70-o1025-Isup2.hkl^{(150.5KB, hkl)}

Click here for additional data file.^{(4.8KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814017280/tk5332Isup3.cml

Click here for additional data file.^{(4.1MB, tif)}

. DOI: 10.1107/S1600536814017280/tk5332fig1.tif

The molecular structure of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.

Click here for additional data file.^{(4.1MB, tif)}

. DOI: 10.1107/S1600536814017280/tk5332fig2.tif

Arrangement between planes within the molecule.

CCDC reference: 1016203

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H71⋯O2ⁱ	0.96	2.54	3.434 (2)	155
C3—H3⋯O3ⁱⁱ	0.93	2.60	3.479 (2)	158

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

Acknowledgments

The authors thank the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) and the Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul (FAPERGS) for financial support and fellowships (PIBIC and PROBIC).

supplementary crystallographic information

S1. Comment

Ethyl-4-aryl-4-methoxy-2-oxo-3-butenoates are interesting precursors for heterocyclic compounds. These 1, 2, 4-trielectrophile systems are synthetic equivalents to 4-aryl-2,4-di,oxobutanoat es (Siddiqui et al., 2013) and were used to produce 1H-pyrazoles (Machado et al., 2007). In the title compound (E)-Ethyl-4-(4-chlorophenyl)-4-methoxy-2-oxo-3-butenoate, C₁₃H₁₃O₄Cl, the whole molecule matches the asymmetric unit (Fig. 1). The molecule presents two almost planar sites (Fig. 2): C7/O1/C8/C9/C10/O2/C11/O3/O4/C12/C13 showed a r.m.s. value of 0.0975 Å with maximum deviation from the mean plane observed for O2 (0.1865 (14) Å). The dihedral angle of 54.10 (5)° confirms that these two fragments are not perfectly perpendicular, suggesting probably the influence of the crystal packing. In the solid state, molecules are connected only through weak non-classical hydrogen bond interactions of the type C—H···O (Thakur et al., 2010), Table 1, generating a supramolecular layer in the ac plane.

S2. Experimental

To a stirred solution of ethyl oxalyl chloride (4.6 ml, 41 mmol) in dry CHCl₃ (25 ml) at 0 °C, a solution containing the acetal (20 mmol), CHCl₃ (15 ml) and pyridine (3.25 ml, 41 mmol) were added dropwise. The mixture was left to cool for at least 1 h, then was allowed to warm to room temperature and refluxed for 5 h. The mixture was washed with distilled water (3 times 10 ml) and dried over Na₂SO₄. The solvent was evaporated and methyl ethyl oxalate formed was distilled at 80 °C (10 mbar) and solid residue was recrystallized from a diluted solution CHCl₃. Yield: 14.8 mmol (74%); M.pt: 85–87 °C; ¹H NMR (400 MHz, CDCl₃): δ 1.31 (t, 3H, CH₃), 3.95 (s, 3H, OCH₃), 4.17 (q, 2H, OCH₂), 6.28 (s, 1H, C9—H), 7.37 (m, 2H, Ph), 7.43 (m, 2H, Ph); ¹³C NMR (100 MHz, CDCl₃): δ p.p.m. 13.8 (CH₃), 57.1 (OCH₃), 62.1 (OCH₂), 96.7 (C9), 128.1, 130.5, 132.5, 136.9 (Ph), 163.2 (C11), 174.4 (C8), 180.9 (C10).