(E)-Methyl 3-(4-chloro­phen­yl)-2-{2-[(E)-(hy­droxy­imino)­meth­yl]phen­oxy­meth­yl}acrylate

K SakthiMurugesan; E Govindan; J Srinivasan; M Bakthadoss; A SubbiahPandi

doi:10.1107/S1600536811038372

. 2011 Sep 30;67(Pt 10):o2754. doi: 10.1107/S1600536811038372

(E)-Methyl 3-(4-chlorophenyl)-2-{2-[(E)-(hydroxyimino)methyl]phenoxymethyl}acrylate

K SakthiMurugesan ^a, E Govindan ^a, J Srinivasan ^b, M Bakthadoss ^b, A SubbiahPandi ^a,^*

PMCID: PMC3201559 PMID: 22064839

Abstract

In the title compound, C₁₈H₁₆ClNO₄, the dihedral angle between the mean planes through the aromatic rings is 83.8 (8)°. The hydroxyethanimine group is essentially coplanar with the ring to which it is attached [O—N—C—C torsion angle = −177.96 (13)°]. The molecules are linked into centrosymmetric R ₂ ²(6) dimers via O—H⋯N hydrogen bonds. The crystal packing is further stabilized by C—H⋯O interactions.

Related literature

For the biological activity of caffeic acids, see: Hwang et al. (2001 ▶); Altug et al. (2008 ▶); Ates et al. (2006 ▶); Atik et al. (2006 ▶); Padinchare et al. (2001 ▶). For the use of oxime ligands in coordination chemistry, see: Chaudhuri (2003 ▶). For related structures, see: Wang et al. (2011 ▶); Govindan et al. (2011 ▶).

Experimental

Crystal data

C₁₈H₁₆ClNO₄
M _r = 345.77
Triclinic,
a = 8.8860 (4) Å
b = 9.3428 (5) Å
c = 12.1494 (6) Å
α = 72.289 (3)°
β = 74.319 (2)°
γ = 63.429 (2)°
V = 848.63 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.25 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
22640 measured reflections
6056 independent reflections
4013 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.161
S = 1.04
6056 reflections
219 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.51 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: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811038372/bt5635sup1.cif

e-67-o2754-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038372/bt5635Isup2.hkl

e-67-o2754-Isup2.hkl^{(290.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811038372/bt5635Isup3.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1ⁱ	0.82	2.12	2.8309 (16)	145
C15—H15⋯O3ⁱⁱ	0.93	2.38	3.186 (2)	145

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

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 antiinflammatory properties (Atik et al., 2006; Padinchare et al., 2001; Ates et al., 2006). Oximes are a classical type of chelating ligands which are widely used in coordination and analytical chemistry (Chaudhuri, 2003). Against this background, and in order to obtain detailed information on molecular conformations in the solid state, an X-ray study of the title compound was carried out.

X-Ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig. 1. The bond lengths and angles in (Fig. 1) agree with those observed in other acrylate derivatives (Wang et al., 2011). The whole molecule is not planar as the dihedral angle between the two phenyl rings is 83.8 (8)°, it shows that both the rings are almost perpendicular to each other. The methoxybutene group connects the two phenyl rings, results in twisting the rings and placed those rings in perpendicular direction. The oxime group having the C═N forming an E configuration. The atom Cl1 is deviated by 0.060 (1)Å from the least squares plane of the C13—C18 ring. The hydroxyethanimine group is essentially coplanar with the benzene ring, the largest deviation from the mean plane being 0.014 (1)Å for the C1 atom.

The enoate group assumes an extended conformation as can be seen from torsion angles C9—C10—O4—C11 [179.3 (1) °] and C12—C9—C10—O4 [-168.9 (1) °]. The hydroxyethanimine group in the molecules are linked into cyclic centrosymmetric dimers via O—H···N hydrogen bonds with the motif R₂²(6). In addition to van der Waals interaction, the crystal packing is stabilized by C–H..O and O–H···N interactions.

Experimental

To a stirred solution of (E)-methyl 2-((2-formylphenoxy) methyl)-3-(4-chlorophenyl)acrylate (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)-methyl3- (4-chlorophenyl)-2-((2-((E)-(hydroxyimino)methyl)phenoxy)methyl)acrylate as a colourless solid. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the title compound in acetone at room temperature.