(Z)-Methyl 2-[(4-bromo-2-formyl­phen­oxy)meth­yl]-3-o-tolyl­acrylate

S Vijayakumar; R Madhanraj; S Murugavel; R Selvakumar; M Bakthadoss

doi:10.1107/S1600536811037731

. 2011 Sep 20;67(Pt 10):o2690. doi: 10.1107/S1600536811037731

(Z)-Methyl 2-[(4-bromo-2-formylphenoxy)methyl]-3-o-tolylacrylate

S Vijayakumar ^a, R Madhanraj ^b, S Murugavel ^c,^*, R Selvakumar ^d, M Bakthadoss ^d

PMCID: PMC3201264 PMID: 22065120

Abstract

In the title compound, C₁₉H₁₇BrO₄, the dihedral angle between the two benzene rings is 82.1 (1)°. The molecular structure is stabilized by an intramolecular C—H⋯O hydrogen bond which generates an S(7) ring motif. The crystal packing is stabilized by intermolecular C—H⋯O hydrogen bonds and C—H⋯π interactions. Intermolecular C—H⋯O interactions are involved in the formation of centrosymmetric R ₂ ²(16) dimers, which are connected into supramolecular tapes running along the [100] direction.

Related literature

For background to the applications of acrylates, see: de Fraine et al. (1991 ▶); Zhang & Ji (1992 ▶). For related structures, see: Wang et al. (2011 ▶); Hou (2008 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₉H₁₇BrO₄
M _r = 389.24
Triclinic,
a = 8.0114 (2) Å
b = 8.6138 (2) Å
c = 13.4827 (4) Å
α = 96.466 (1)°
β = 97.185 (1)°
γ = 106.546 (2)°
V = 874.08 (4) Å³
Z = 2
Mo Kα radiation
μ = 2.37 mm⁻¹
T = 293 K
0.25 × 0.23 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.547, T _max = 0.653
21788 measured reflections
5440 independent reflections
2870 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.125
S = 1.02
5440 reflections
219 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811037731/bt5640sup1.cif

e-67-o2690-sup1.cif^{(19KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037731/bt5640Isup2.hkl

e-67-o2690-Isup2.hkl^{(261KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811037731/bt5640Isup3.cml

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

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

Cg is the centroid of the C13–C18 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O3	0.93	2.59	3.377 (3)	143
C19—H19B⋯O1ⁱ	0.96	2.53	3.436 (3)	157
C5—H5⋯O4ⁱⁱ	0.93	2.44	3.273 (3)	149
C19—H19C⋯Cgⁱⁱⁱ	0.96	2.74	3.580 (3)	147

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

Acknowledgments

SM thanks Dr Babu Vargheese, SAIF, IIT, Madras, India, for his help with the data collection.

supplementary crystallographic information

Comment

Acrylate and its derivatives are important compounds because of their agrochemical and medical applications (de Fraine et al., 1991; Zhang & Ji, 1992).

Fig. 1. shows a displacement ellipsoid plot of the title compound with the atom numbering scheme. The dihedral angle between the two aromatic rings is 82.1 (1)°. The methyl acrylate (O1/O2/C7-C10) plane forms dihedral angles of 84.9 (1)° and 41.5 (1)°, respectively, with the bromo formyl phenyl and methyl phenyl rings. The geometric parameters of the title molecule agrees well with those reported for similar structures (Wang et al., 2011; Hou, 2008).

The molecular structure is stabilized by intramolecular C14—H14···O3 hydrogen bond which generates an S(7) ring motif. The crystal packing is stabilized by intermolecular C—H···O hydrogen bonds. The molecules at x, y, z and 1-x, -y, -z are linked by C19—H19B···O1 hydrogen bonds into cyclic centrosymmetric R₂²(16) dimers. The dimers are linked by the C5—H5···O4 hydrogen bond forming supramolecular tapes running along the [100] directions (Fig. 2). The crystal packing is further stabilized by C—H···π interactions between a methyl H19C atom and a neighbouring benzene ring (C13-C18), with a C19—H19C···Cgⁱⁱⁱ separation of 2.74 Å ( Fig. 3 and Table 1; Cg is the centroid of the C13-C18 benzene ring, Symmetry code as in Fig. 3).

Experimental

A solution of salicylaldehyde (3.7 mmol, 0.74g) and potassium carbonate (5.59 mmol, 0.77g) in acetonitrile as solvent (10ml) was stirred for 15 minutes at room temperature. To this solution, (Z-methyl 2-(bromomethyl)-3-o-tolylacrylate (3.7 mmol, 1g) was added dropwise. After the completion of the reaction as indicated by TLC, acetonitrile was evaporated. Ethylacetate (15ml) and water (15ml) were added to the crude mass and extracted. The organic layer was dried over anhydrous sodium sulfate. Removal of the solvent led to the crude product which was purified through pad of silica gel (100-200 mesh) using ethylacetate and hexanes (1:9) as solvents. The pure title compound was obtained as a colorless solid (1.32g, 91%). Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a ethylacetate solution at room temperature.