Ethyl (2E)-2-cyano-3-(4-meth­oxy­phen­yl)acrylate

P A Suchetan; B S Palakshamurthy; N R Mohan; S Madan Kumar; N K Lokanath; S Sreenivasa

doi:10.1107/S1600536813026871

. 2013 Oct 5;69(Pt 11):o1610. doi: 10.1107/S1600536813026871

Ethyl (2E)-2-cyano-3-(4-methoxyphenyl)acrylate

P A Suchetan ^a, B S Palakshamurthy ^b, N R Mohan ^c, S Madan Kumar ^d, N K Lokanath ^d, S Sreenivasa ^c,^*

PMCID: PMC3884285 PMID: 24454061

Abstract

In the title compound, C₁₃H₁₃NO₃, the conformation across the C=C bond is synperiplanar, the torsion angle of the segment C(ring)—C=C—C(N) being 3.2 (5)°. In the crystal, molecules are linked into inversion dimers, arranged in a zigzag pattern, through two C—H⋯O interactions generating R ₂ ²(10) and R ₂ ²(14) motifs. These dimers are arranged in a zigzag pattern in the crystal structure. The molecules are further linked along the c axis through weak C—H⋯π interactions, and weak π⋯π interactions [centroid–centroid separation = 3.9986 (17) Å] are also observed.

Related literature

For use of the title compound in the synthesis of prop-2-enoylamides, see: Santos et al.. (2004 ▶). For use of the title compound in the synthesis of prop-2-enoates, see: Sousa et al. (2006 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). graphic file with name e-69-o1610-scheme1.jpg

Experimental

Crystal data

C₁₃H₁₃NO₃
M _r = 231.24
Monoclinic,
a = 8.4889 (12) Å
b = 8.3552 (16) Å
c = 17.143 (3) Å
β = 91.294 (11)°
V = 1215.6 (3) Å³
Z = 4
Cu Kα radiation
μ = 0.74 mm⁻¹
T = 296 K
0.40 × 0.33 × 0.27 mm

Data collection

Bruker APEXII CCD diffractometer
4798 measured reflections
1937 independent reflections
1354 reflections with I > 2σ(I)
R _int = 0.069

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.201
S = 1.02
1937 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: APEX2 and SAINT-Plus (Bruker, 2009 ▶); data reduction: SAINT-Plus and XPREP; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813026871/sj5355sup1.cif

e-69-o1610-sup1.cif^{(20.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813026871/sj5355Isup2.hkl

e-69-o1610-Isup2.hkl^{(93.4KB, hkl)}

Click here for additional data file.^{(4.6KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813026871/sj5355Isup3.cml

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

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

Cg is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2ⁱ	0.93	2.54	3.414 (3)	157
C8—H8⋯O2ⁱ	0.93	2.59	3.475 (3)	159
C12—H12A⋯Cg ⁱⁱ	0.97	2.90	3.803 (3)	156

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

Acknowledgments

The authors acknowledge the IOE X-ray diffractometer Facility, University of Mysore, Mysore, for the data collection.

supplementary crystallographic information

1. Comment

Ethyl (2E)-2-cyano-3-(4-methoxyphenyl)acrylate is an important starting material for the synthesis of biologically and pharmacologically important 2-propenoylamides (Santos et al.., 2004) and 2-propenoates (Sousa et al., 2006). Keeping this in mind, the title compound was synthesized.

In the title compound, C₁₃H₁₃NO₃, the conformation across the C=C bond is syn-periplanar (Fig.1), the C4—C8—C9—C10 torsion angle being 3.2 (5)°. The molecules are linked into inversion dimers (Fig.2) through C3—H3···O2 and C8—H8···O2 interactions, generating R₂²(10) and R₂²(14) ring motifs (Bernstein et al., 1995). These dimers are arranged in a zigzag pattern in the crystal structure (Fig.3). The molecules are further linked along the c axis through weak C12—H12A···Cg interactions (Fig.4), and weak Cg···Cg interactions (centroid···centroid separation = 3.9986 (17) Å) are also observed (Fig.5).

2. Experimental

A mixture of tetra-n-butylammonium bromide (TBAB) (3.47 g, 10 mmol), palladium acetate (0.060 g, 0.27 mmol), triphenylphosphine (2.97 g, 11 mmol), 1-bromo-4-methoxybenzene (1 g, 5.4 mmol) and potassium carbonate (1.12 g, 8.1 mmol) were dissolved in 10 ml of DMF in a three-necked round bottom flask and the reaction mixture was heated to 120 °C under nitrogen atmosphere with constant stirring for 10–15 minutes until a yellowish brown solution was obtained. Ethyl-2-cyanoacrylate (0.81 g, 6.4 mmol) was added to the solution and the reaction mixture was heated to 120 °C for 10 h, cooled and filtered under vacuum to obtain the crude compound. This was further purified by column chromatography using petroleum ether: ethyl acetate (7:3) as eluent (Rf value = 0.69), to yield pale green colored crystals.