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Acta Crystallogr Sect E Struct Rep Online. Feb 1, 2012; 68(Pt 2): o484.
Published online Jan 21, 2012. doi:  10.1107/S1600536812001481
PMCID: PMC3275232
(E)-2-({2-[(E)-(Hy­droxy­imino)­meth­yl]phen­oxy}meth­yl)-3-o-tolyl­acrylonitrile
E. Govindan,a J. Srinivasan,b M. Bakthadoss,b and A. SubbiahPandia*
aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India
bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
Correspondence e-mail: a_sp59/at/yahoo.in
Received January 5, 2012; Accepted January 12, 2012.
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 [triangle]). For the use of oximes as chelating ligands in coordination and analytical chemistry, see: Chaudhuri et al. (2003 [triangle]). For a related structure, see: Govindan et al. (2011 [triangle]).
An external file that holds a picture, illustration, etc.
Object name is e-68-0o484-scheme1.jpg Object name is e-68-0o484-scheme1.jpg
Crystal data
  • C18H16N2O2
  • M r = 292.33
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-0o484-efi2.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.19 e Å−3
Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 [triangle]).
Table 1
Table 1
Hydrogen-bond geometry (Å, °)
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812001481/qm2049sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812001481/qm2049Isup2.hkl
Supplementary material file. DOI: 10.1107/S1600536812001481/qm2049Isup3.cml
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
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.
Refinement
All H atoms were fixed geometrically and allowed to ride on their parent C atoms, with C—H distances fixed in the range 0.93–0.97 Å with Uiso(H) = 1.5Ueq(C) for methyl H 1.2Ueq(C) for other H atoms.
Figures
Fig. 1.
Fig. 1.
View of the title molecule with the atom labelling scheme. The displacement ellipsoids are drawn at the 30% probability level while the H atoms are shown as small spheres of arbitrary radii.
Fig. 2.
Fig. 2.
The crystal structure showing the centrosymmetric hydrogen bond motif R22(6). For the sake of clarity, the H atoms not involved in the motif have been omitted. The atoms marked with an asterisk (*) are at the symmetry position (-1 - x, -y, 1 - z). The (more ...)
Crystal data
C18H16N2O2Z = 2
Mr = 292.33F(000) = 308
Triclinic, P1Dx = 1.247 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.0214 (2) ÅCell parameters from 5557 reflections
b = 10.5094 (3) Åθ = 1.9°
c = 10.8854 (3) ŵ = 0.08 mm1
α = 97.636 (1)°T = 293 K
β = 95.953 (1)°Block, white crystalline
γ = 99.642 (1)°0.25 × 0.22 × 0.19 mm
V = 778.32 (4) Å3
Data collection
Bruker APEXII CCD area-detector diffractometer5557 independent reflections
Radiation source: fine-focus sealed tube3825 reflections with I > 2σ(I)
graphiteRint = 0.029
ω and [var phi] scansθmax = 34.6°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→11
Tmin = 0.978, Tmax = 0.983k = −16→15
21189 measured reflectionsl = −16→16
Refinement
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.163H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.0845P)2 + 0.0621P] where P = (Fo2 + 2Fc2)/3
5557 reflections(Δ/σ)max < 0.001
201 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = −0.18 e Å3
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
xyzUiso*/Ueq
C1−0.15593 (16)0.00826 (11)0.65422 (11)0.0458 (3)
H1−0.11820.07600.72100.055*
C2−0.02936 (15)−0.08709 (10)0.63051 (10)0.0403 (2)
C3−0.08597 (19)−0.20010 (12)0.54286 (12)0.0537 (3)
H3−0.2068−0.21480.49430.064*
C40.0343 (2)−0.29046 (12)0.52696 (13)0.0590 (3)
H4−0.0051−0.36490.46740.071*
C50.21237 (19)−0.27051 (12)0.59921 (12)0.0536 (3)
H50.2919−0.33270.58970.064*
C60.27362 (17)−0.15902 (11)0.68554 (11)0.0465 (3)
H60.3947−0.14550.73370.056*
C70.15422 (14)−0.06683 (10)0.70047 (9)0.0381 (2)
C80.34958 (15)0.05707 (11)0.88418 (10)0.0430 (2)
H8A0.47950.07290.85980.052*
H8B0.3317−0.02400.91870.052*
C90.32336 (14)0.16826 (10)0.97920 (10)0.0387 (2)
C100.12321 (15)0.17173 (11)0.99392 (11)0.0467 (3)
C110.47398 (14)0.25582 (10)1.04165 (10)0.0395 (2)
H110.59580.24501.02030.047*
C120.47398 (15)0.36647 (10)1.13905 (10)0.0399 (2)
C130.3269 (2)0.36659 (13)1.21596 (12)0.0552 (3)
H130.22990.29301.20870.066*
C140.3234 (2)0.47427 (15)1.30267 (15)0.0735 (4)
H140.22380.47351.35270.088*
C150.4678 (3)0.58260 (15)1.31470 (16)0.0760 (5)
H150.46420.65631.37140.091*
C160.6170 (2)0.58189 (12)1.24310 (14)0.0609 (3)
H160.71490.65541.25330.073*
C170.62672 (16)0.47510 (11)1.15593 (11)0.0441 (2)
C180.79547 (18)0.47851 (14)1.08190 (15)0.0597 (3)
H18A0.88110.56161.10460.090*
H18B0.74840.46570.99430.090*
H18C0.86510.41041.09930.090*
N1−0.31578 (13)0.00044 (10)0.58572 (9)0.0461 (2)
N2−0.03874 (16)0.17076 (12)0.99832 (14)0.0698 (4)
O1−0.41663 (12)0.09866 (9)0.62794 (9)0.0605 (3)
H1A−0.51630.09350.57970.091*
O20.20712 (11)0.04926 (7)0.77921 (7)0.0467 (2)
Atomic displacement parameters (Å2)
U11U22U33U12U13U23
C10.0381 (5)0.0484 (6)0.0469 (6)0.0088 (4)−0.0016 (4)−0.0025 (5)
C20.0366 (5)0.0415 (5)0.0403 (5)0.0061 (4)0.0010 (4)0.0014 (4)
C30.0508 (6)0.0495 (6)0.0520 (7)0.0048 (5)−0.0073 (5)−0.0076 (5)
C40.0703 (8)0.0439 (6)0.0553 (7)0.0082 (6)0.0010 (6)−0.0108 (5)
C50.0648 (7)0.0449 (6)0.0527 (7)0.0205 (5)0.0097 (6)−0.0010 (5)
C60.0455 (6)0.0466 (6)0.0471 (6)0.0159 (5)0.0017 (4)0.0005 (5)
C70.0387 (5)0.0371 (5)0.0368 (5)0.0077 (4)0.0022 (4)0.0004 (4)
C80.0359 (5)0.0443 (5)0.0456 (6)0.0138 (4)−0.0041 (4)−0.0056 (4)
C90.0350 (4)0.0378 (5)0.0422 (5)0.0098 (4)0.0021 (4)−0.0002 (4)
C100.0386 (5)0.0400 (5)0.0571 (7)0.0063 (4)0.0048 (5)−0.0061 (5)
C110.0360 (5)0.0395 (5)0.0415 (5)0.0082 (4)0.0023 (4)0.0015 (4)
C120.0402 (5)0.0369 (5)0.0403 (5)0.0070 (4)0.0004 (4)0.0008 (4)
C130.0579 (7)0.0501 (6)0.0516 (7)−0.0010 (5)0.0152 (5)−0.0060 (5)
C140.0811 (10)0.0672 (9)0.0675 (9)0.0059 (7)0.0313 (8)−0.0141 (7)
C150.0977 (12)0.0526 (8)0.0692 (9)0.0061 (7)0.0200 (8)−0.0191 (7)
C160.0689 (8)0.0408 (6)0.0638 (8)−0.0020 (6)0.0026 (6)−0.0049 (5)
C170.0426 (5)0.0390 (5)0.0477 (6)0.0057 (4)−0.0020 (4)0.0043 (4)
C180.0435 (6)0.0541 (7)0.0775 (9)−0.0001 (5)0.0086 (6)0.0063 (6)
N10.0370 (4)0.0491 (5)0.0508 (5)0.0111 (4)0.0010 (4)0.0023 (4)
N20.0416 (5)0.0669 (7)0.0954 (9)0.0107 (5)0.0122 (5)−0.0110 (6)
O10.0460 (5)0.0644 (6)0.0689 (6)0.0224 (4)−0.0026 (4)−0.0054 (4)
O20.0442 (4)0.0416 (4)0.0490 (4)0.0146 (3)−0.0114 (3)−0.0076 (3)
Geometric parameters (Å, °)
C1—N11.2655 (14)C10—N21.1415 (15)
C1—C21.4621 (14)C11—C121.4658 (13)
C1—H10.9300C11—H110.9300
C2—C31.3932 (15)C12—C131.3950 (16)
C2—C71.3958 (14)C12—C171.4074 (16)
C3—C41.3783 (18)C13—C141.3793 (17)
C3—H30.9300C13—H130.9300
C4—C51.3751 (19)C14—C151.374 (2)
C4—H40.9300C14—H140.9300
C5—C61.3768 (16)C15—C161.369 (2)
C5—H50.9300C15—H150.9300
C6—C71.3880 (14)C16—C171.3859 (16)
C6—H60.9300C16—H160.9300
C7—O21.3658 (12)C17—C181.4987 (17)
C8—O21.4225 (12)C18—H18A0.9600
C8—C91.5032 (13)C18—H18B0.9600
C8—H8A0.9700C18—H18C0.9600
C8—H8B0.9700N1—O11.4016 (12)
C9—C111.3364 (14)O1—H1A0.8200
C9—C101.4367 (14)
N1—C1—C2121.33 (10)C9—C11—C12129.04 (9)
N1—C1—H1119.3C9—C11—H11115.5
C2—C1—H1119.3C12—C11—H11115.5
C3—C2—C7118.07 (10)C13—C12—C17119.11 (10)
C3—C2—C1122.78 (10)C13—C12—C11121.69 (10)
C7—C2—C1119.13 (9)C17—C12—C11119.20 (10)
C4—C3—C2121.07 (11)C14—C13—C12120.96 (12)
C4—C3—H3119.5C14—C13—H13119.5
C2—C3—H3119.5C12—C13—H13119.5
C5—C4—C3119.99 (11)C15—C14—C13119.68 (13)
C5—C4—H4120.0C15—C14—H14120.2
C3—C4—H4120.0C13—C14—H14120.2
C4—C5—C6120.34 (11)C16—C15—C14119.93 (12)
C4—C5—H5119.8C16—C15—H15120.0
C6—C5—H5119.8C14—C15—H15120.0
C5—C6—C7119.82 (11)C15—C16—C17122.09 (12)
C5—C6—H6120.1C15—C16—H16119.0
C7—C6—H6120.1C17—C16—H16119.0
O2—C7—C6123.73 (9)C16—C17—C12118.08 (11)
O2—C7—C2115.58 (8)C16—C17—C18119.87 (11)
C6—C7—C2120.66 (10)C12—C17—C18122.04 (10)
O2—C8—C9107.03 (8)C17—C18—H18A109.5
O2—C8—H8A110.3C17—C18—H18B109.5
C9—C8—H8A110.3H18A—C18—H18B109.5
O2—C8—H8B110.3C17—C18—H18C109.5
C9—C8—H8B110.3H18A—C18—H18C109.5
H8A—C8—H8B108.6H18B—C18—H18C109.5
C11—C9—C10124.04 (9)C1—N1—O1111.76 (9)
C11—C9—C8122.27 (9)N1—O1—H1A109.5
C10—C9—C8113.68 (9)C7—O2—C8118.07 (8)
N2—C10—C9175.85 (13)
N1—C1—C2—C3−8.33 (19)C8—C9—C11—C12−177.93 (10)
N1—C1—C2—C7173.47 (11)C9—C11—C12—C1326.68 (19)
C7—C2—C3—C41.03 (19)C9—C11—C12—C17−153.67 (12)
C1—C2—C3—C4−177.18 (13)C17—C12—C13—C143.8 (2)
C2—C3—C4—C50.8 (2)C11—C12—C13—C14−176.50 (13)
C3—C4—C5—C6−1.6 (2)C12—C13—C14—C15−0.7 (3)
C4—C5—C6—C70.57 (19)C13—C14—C15—C16−1.8 (3)
C5—C6—C7—O2−176.62 (11)C14—C15—C16—C171.1 (3)
C5—C6—C7—C21.26 (18)C15—C16—C17—C122.0 (2)
C3—C2—C7—O2176.01 (10)C15—C16—C17—C18−178.74 (15)
C1—C2—C7—O2−5.71 (15)C13—C12—C17—C16−4.40 (18)
C3—C2—C7—C6−2.03 (17)C11—C12—C17—C16175.94 (11)
C1—C2—C7—C6176.25 (10)C13—C12—C17—C18176.37 (12)
O2—C8—C9—C11−135.77 (11)C11—C12—C17—C18−3.29 (17)
O2—C8—C9—C1043.22 (13)C2—C1—N1—O1177.80 (10)
C11—C9—C10—N2151.8 (19)C6—C7—O2—C8−25.64 (15)
C8—C9—C10—N2−27 (2)C2—C7—O2—C8156.39 (10)
C10—C9—C11—C123.19 (19)C9—C8—O2—C7−157.61 (9)
Hydrogen-bond geometry (Å, °)
D—H···AD—HH···AD···AD—H···A
O1—H1A···N1i0.822.072.7962 (13)147
Symmetry codes: (i) −x−1, −y, −z+1.
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: QM2049).
References
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