(E)-Methyl 2-({2-eth­oxy-6-[(E)-(hy­droxy­imino)­meth­yl]phen­oxy}meth­yl)-3-phenyl­acrylate

E Govindan; G Ganesh; J Srinivasan; M Bakthadoss; A SubbiahPandi

doi:10.1107/S1600536812014596

. 2012 Apr 13;68(Pt 5):o1373. doi: 10.1107/S1600536812014596

(E)-Methyl 2-({2-ethoxy-6-[(E)-(hydroxyimino)methyl]phenoxy}methyl)-3-phenylacrylate

E Govindan ^a, G Ganesh ^b, J Srinivasan ^c, M Bakthadoss ^c, A SubbiahPandi ^a,^*

PMCID: PMC3344504 PMID: 22590266

Abstract

In the title compound, C₂₀H₂₁NO₅, the dihedral angle between the mean planes through the two rings is 47.1 (8)°. The enoate group assumes an extended conformation. The hydroxyethanimine group is essentially coplanar with the benzene ring, the largest deviation from the mean plane being 0.061 (1) Å for the O atom. In the crystal, molecules are linked into cyclic centrosymmetric dimers with an R ₂ ²(6) motif via pairs of O—H⋯N hydrogen bonds. Intermolecular C—H⋯O hydrogen bonds form a C(8) chain along the b axis. The crystal packing is further stabilized by C—H⋯π interactions.

Related literature

For the biological activity of caffeic acids and their esters, see: Hwang et al. (2001 ▶); Altug et al. (2008 ▶); Ates et al. (2006 ▶); Atik et al. (2006 ▶); Chaudhuri (2003 ▶); Padinchare et al. (2001 ▶). For a related structure, see: SakthiMurugesan et al. (2011 ▶). For graph-set analysis of hydrogen bonds, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₀H₂₁NO₅
M _r = 355.38
Monoclinic,
a = 7.4009 (3) Å
b = 22.1125 (10) Å
c = 11.3681 (5) Å
β = 103.561 (1)°
V = 1808.55 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.25 × 0.22 × 0.19 mm

Data collection

Bruker APEXII CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.978, T _max = 0.983
25247 measured reflections
6042 independent reflections
4293 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.167
S = 1.02
6042 reflections
238 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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 (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/S1600536812014596/rn2100sup1.cif

e-68-o1373-sup1.cif^{(20.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014596/rn2100Isup2.hkl

e-68-o1373-Isup2.hkl^{(289.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812014596/rn2100Isup3.cml

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

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

Cg2 is the centroid of the C15–C20 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1ⁱ	0.82	2.08	2.8121 (15)	149
C4—H4⋯O4ⁱⁱ	0.93	2.59	3.2379 (18)	127
C20—H20⋯O1ⁱⁱⁱ	0.93	2.59	3.466 (2)	157
C9—H9B⋯Cg2^iv	0.96	2.79	3.616 (2)	145

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

Acknowledgments

EG and ASP thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.

supplementary crystallographic information

Comment

Some naturally occurring caffeic acids and their esters attract much attention in biology and medicine (Hwang et al., 2001; Altug et al., 2008). These compounds show antiviral, antibacterial, vasoactive, antiatherogenic, antiproliferative, antioxidant and anti-inflammatory properties (Atik et al., 2006; Padinchare et al., 2001; Ates et al., 2006). Oximes are a classical type of chelating ligand which are widely used in coordination and analytical chemistry (Chaudhuri, 2003).

In the title compound (see Fig. 1) the bond lengths and angles agree with those observed in other acrylate derivatives (SakthiMurugesan et al., 2011). The whole molecule is not planar as the dihedral angle between the two phenyl rings is 47.1 (8)°. The oxime C—N has an E configuration. The hydroxyethanimine group is essentially coplanar with the benzene ring, the largest deviation from the mean plane being 0.004 (1) Å for the C2 atom.

The ether group assumes an extended conformation as can be seen from torsion angles C11—C12—O5—C13 [-174.7 (1) °] and C10—C11—C12—O5 [170.7 (1) °]. C—H···O hydrogen bonds (see Table 1) form C(8) chains along (Bernstein et al. 1995) the b axis. The hydroxyethanimine group in the molecules are linked into cyclic centrosymmetric dimers via O—H···N hydrogen bonds with the R₂²(6) motif. The closest C—H-centroid separation is 3.6 Å therefore there are not significant C—H···π interactions. In addition to van der Waals interactions the crystal packing is stabilized by C–H···O and O–H···N interactions.

Experimental

To a stirred solution of (E)-methyl 2-((2-ethoxy-6-formylphenoxy)methyl) -3-phenylacrylate (4 mmol) in 10 ml of EtOH/H₂O mixture (1:1) was added NH₂OH.HCl (6 mmol) in the presence of 50% NaOH at room temperature. Then the reaction mixture was allowed to stir at room temperature for 1.5 h. After completion of the reaction, solvent was removed and the crude mass was diluted with water (15 ml) and extracted with ethyl acetate (3 x 15 ml). The combined organic layer was washed with brine (2 x 10 ml) and dried over anhydrous Na₂SO₄ and then evaporated under reduced pressure to obtain (E)-methyl2-((2-ethoxy- 6-((E)-(hydroxyimino)methyl)phenoxy)methyl)-3-phenylacrylate as a colourless solid.