(E)-2-({2-[(E)-(Hy­droxy­imino)­meth­yl]phen­oxy}meth­yl)-3-o-tolyl­acrylonitrile

E Govindan; J Srinivasan; M Bakthadoss; A SubbiahPandi

doi:10.1107/S1600536812001481

. 2012 Jan 21;68(Pt 2):o484. doi: 10.1107/S1600536812001481

(E)-2-({2-[(E)-(Hydroxyimino)methyl]phenoxy}methyl)-3-o-tolylacrylonitrile

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

PMCID: PMC3275232 PMID: 22347088

Abstract

In the title compound, C₁₈H₁₆N₂O₂, the dihedral angle between the mean planes through the two benzene rings is 56.8 (6)°. 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 0.047 (1) Å for the hydroxyimino O atom. In the crystal, the molecules are linked into cyclic centrosymmetric dimers with R ₂ ²(6) motifs via O—H⋯N hydrogen bonds.

Related literature

For the use of 2-cyanoacrylates and oximes as agrochemicals, see: Zhang et al. (2009 ▶). For the use of oximes as chelating ligands in coordination and analytical chemistry, see: Chaudhuri et al. (2003 ▶). For a related structure, see: Govindan et al. (2011 ▶).

Experimental

Crystal data

C₁₈H₁₆N₂O₂
M _r = 292.33
Triclinic,
a = 7.0214 (2) Å
b = 10.5094 (3) Å
c = 10.8854 (3) Å
α = 97.636 (1)°
β = 95.953 (1)°
γ = 99.642 (1)°
V = 778.32 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.08 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
21189 measured reflections
5557 independent reflections
3825 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.163
S = 1.06
5557 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.19 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/S1600536812001481/qm2049sup1.cif

e-68-0o484-sup1.cif^{(18.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812001481/qm2049Isup2.hkl

e-68-0o484-Isup2.hkl^{(266.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812001481/qm2049Isup3.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	2.07	2.7962 (13)	147

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.

supplementary crystallographic information

Comment

Recently, 2-cyanoacrylates have been extensively used as agrochemicals because of their unique mechanism of action and good environmental profiles (Zhang et al., 2009). 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 tolylacrylonitile derivatives (Govindan et al., 2011). The whole molecule is not planar as the dihedral angle between the two phenyl rings is 56.8 (6)°, The oxime group having the C=N forming an E configuration. The hydroxyethanimine group is essentially coplanar with the benzene ring, the largest deviation from the mean plane of the hydroxyethanimine [C=N—OH] group is 0.047 (1) Å. for the O1 atom.

The enoate group assumes an extended conformation as can be seen from torsion angles C2—C1—N1—O1 [177.9 (2)°] and C1—C2—C3—C4 [-177.1 (2) °]. The atom C15 in the molecule (x,y,z) donate one proton to atom O1 of the molecule at (-1 - x,-y,1 - z) forming a C(6) chain along b axis. The hydroxyethanimine group in the molecules are linked into cyclic centrosymmetric dimers via O—H···N hydrogen bonds with the motif R²₂(6) (Fig. 2). In addition to van der Waals interaction, the crystal packing is stabilized by C—H···O interactions.

Experimental

To a stirred solution of (E)-2-((2-formylphenoxy)methyl)-3-o- tolylacrylonitrile (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 (2E)-2-((2-((Hydroxyimino)methyl) phenoxy)methyl)-3-o-tolylacrylonitrile as a colourless solid.