Methyl (E)-3-(2-formyl­phen­oxy)acrylate

S Karthikeyan; K Sethusankar; R Selvakumar; M Bakthadoss

doi:10.1107/S1600536814010617

. 2014 May 24;70(Pt 6):o709. doi: 10.1107/S1600536814010617

Methyl (E)-3-(2-formylphenoxy)acrylate

S Karthikeyan ^a, K Sethusankar ^a,^*, R Selvakumar ^b, M Bakthadoss ^b

PMCID: PMC4051041 PMID: 24940280

Abstract

In the title compound, C₁₁H₁₀O₄, the methyl acrylate substituent adopts an extended E conformation with all torsion angles close to 180°. The conformation of the keto group with respect to the olefinic double bond is typically S-trans. In the crystal, molecules are linked via pairs of C—H⋯O hydrogen bonds, forming inversion dimers with an R ₂ ²(8) graph-set motif. The dimers are further linked via C—H⋯O hydrogen bonds, forming chains along [001], which enclose R ₃ ²(16) graph-set ring motifs. The keto group O atomaccepts two C—H⋯O interactions.

Related literature

For applications of acrylate derivatives, see: Xiao et al. (2008 ▶); De et al. (2011 ▶); Sharma (2011 ▶). For related crystal structures, see: Karthikeyan et al. (2012 ▶). For E-conformation aspects, see: Dunitz & Schweizer (1982 ▶). For resonance effects of acrylate, see: Merlino (1971 ▶); Varghese et al. (1986 ▶). For graph-set motif notation, see: Bernstein et al. (1995 ▶). graphic file with name e-70-0o709-scheme1.jpg

Experimental

Crystal data

C₁₁H₁₀O₄
M _r = 206.19
Monoclinic,
a = 17.7458 (8) Å
b = 4.0629 (2) Å
c = 14.5745 (7) Å
β = 107.868 (3)°
V = 1000.13 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.20 × 0.15 × 0.10 mm

Data collection

Bruker SMART APEXII CCD diffractometer
13052 measured reflections
2015 independent reflections
1523 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.155
S = 1.06
2015 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814010617/su2732sup1.cif

e-70-0o709-sup1.cif^{(15.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814010617/su2732Isup2.hkl

e-70-0o709-Isup2.hkl^{(99.1KB, hkl)}

Click here for additional data file.^{(4KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814010617/su2732Isup3.cml

CCDC reference: 1001914

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
C9—H9⋯O2ⁱ	0.93	2.54	3.440 (2)	164
C8—H8⋯O4ⁱⁱ	0.93	2.61	3.529 (2)	171
C11—H11C⋯O2ⁱⁱⁱ	0.96	2.63	3.578 (2)	168

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

Acknowledgments

SK and KS thank Dr D. Velmurugan, CAS in Crystallography and Biophysics, University of Madras, Maraimalai Campus, Chennai, India, for the X-ray intensity data collection.

supplementary crystallographic information

1. Comment

Cinnamic acid derivatives have received attention in medicinal research as traditional as well as recent synthetic antitumor agents (De et al., 2011). They also posses significant antibacterial activities against staphylococcus aureus (Xiao et al., 2008). Different substitutions on the basic moiety lead to various pharmacological activities, such as antioxidant, hepatoprotective, anxiolytic, insect repellent, antidiabetic, and anticholesterolemic (Sharma, 2011).

In the title molecule, Fig. 1, the methyl acrylate group is essentially planar, with a maximum deviation of 0.0264 (19) Å for atom C9. Its mean plane forms a dihedral angle of 31.74 (6)° with the benzene ring (C2—C7). The molecular dimensions are in excellent agreement with the those reported for a closely related compound (Karthikeyan et al., 2012).

The configuration of the keto group with respect to the olefinic double bond is typically S-trans, with the O2═C10—C9═C8 torsion angle = 178.78 (19)°. The methyl acrylate group adopts an extended E conformation with torsion angles C8═C9—C10═O2 = 178.78 (19)°, C8═ C9—C10—O1 = -1.2 (3)°, C9—C10—O1—C11 = -178.82 (16)° and O2═ C10—O1—C11 = 1.2 (3)°. The extended conformation is supported by the fact that the bond angles involving carbonyl O atoms are invariably enlarged (Dunitz & Schweizer, 1982).

The significant difference in the bond lengths C10—O1 = 1.342 (2) Å and C11—O1 = 1.438 (2) Å is attributed to a partial contribution from the O^-—C═O⁺—C resonance structure of the O2═C10—O1—C11 group (Merlino, 1971). This feature, commonly observed for the carboxylic ester group of substituents in various compounds gives average values of 1.340 Å and 1.447 Å, respectively (Varghese et al., 1986).

The crystal packing (Fig. 2 and Table 1) is stabilized by C—H···O intermolecular interactions. The molecules are linked into inversion dimers via C9—H9···O2 interactions resulting in an R²₂(8) graph-set motif (Bernstein et al., 1995). The dimers are further consolidated by R²₃(16) graph-set ring motifs via C8—H8···O4 and C11—H11C···O2 interactions resulting in chains of molecules running parallel to the c axis; the keto group O atom (O2) is involved in bifurcated hydrogen bonding.

2. Experimental

Salicylaldehyde (1 mmol) was dissolved in an aqueous solution of K₂CO₃ (1 mmol) and methyl propiolate (1 mmol) was added. The reaction mixture was stirred vigorously at room temperature. A turbid solution was formed by consumption of salicylaldehyde (monitored by TLC) in 5 min, the reaction mixture then became clear. The title compound was precipitated as a solid in water. The product was isolated by filtration without further purification [Yield 75%]. Block-like colourless crystals were obtained by slow evaporation of a solution in ethylacetate.