organic compounds
(E)-4-Methyl-2-(N-phenylcarboximidoyl)phenol
aPostgraduate Research Department of Physics, Government Arts College (Autonomous), Kumbakonam 612 001, Tamilnadu, India, bPostgraduate Department of Physics, Dharmapuram Gnanambigai Government Arts College (Women), Mayiladuthurai 609 001, Tamilnadu, India, cPrincipal, Kunthavai Naacchiyaar Government Arts College for Women (Autonomous), Thanjavur 613 007, Tamilnadu, India, and dPostgraduate Department of Physics, A.D.M. College for Women (Autonomous), Nagapattinam 611 001, Tamilnadu, India
*Correspondence e-mail: thiruvalluvar.a@gmail.com
The title compound, C14H13NO, is not planar with the dihedral angle between the planes of the two aryl rings being 6.22 (11)°. The configuration about the imine bond is E. An intramolecular O—H⋯N hydrogen bond generates an S(6) loop. In the crystal, molecules assemble into columns parallel to the a axis. The methyl group is disordered over two positions rotated from each other by 60°.
CCDC reference: 1831435
Structure description
We report here, as part of our on-going research (Ida Malarselvi et al., 2016; Swetha et al., 2017), the synthesis and the X-ray of the title methylated Schiff base compound, Fig.1, synthesized from the condensation reaction of equimolar amounts of 5-methylsalicylaldehyde and aniline in a mixture of DMSO and CCl4.
The benzene and phenyl rings deviate from co-planarity with the dihedral angle between the two rings being 6.22 (11)°. The molecule has an E configuration about the C=N bond; the C2—C7=N1—C8 torsion angle is −177.73 (17)°. There is an intramolecular O1—H1⋯N1 hydrogen bond with an H⋯N distance of 1.73 (3) Å generating an S(6) loop, see Table 1 and Fig. 1. In the crystal, molecules assemble into columns parallel to the a axis, Fig. 2.
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Swetha et al. (2017) have reported the of (E)-4-fluoro-2-[(phenylimino)methyl]phenol, in which the molecule is essentially planar (r.m.s. deviation = 0.022 Å) and the dihedral angle between the planes of the two aryl rings is 0.69 (15)°.
Synthesis and crystallization
5-Methylsalicylaldehyde (0.64 g, 0.0047 mol) was dissolved in a mixture of DMSO (7.5 ml) and CCl4 (7.5 ml). To this solution, aniline (0.42 g, 0.0045 mol) was added drop-wise with constant stirring for 1 h. During this time, the solution turned deep yellow. On standing for two weeks and with slow evaporation of the solvent, orange crystals of the title compound were deposited.
Refinement
Crystal data, data collection and structure . The methyl group was found to be disordered over two positions rotated from each other by 60°, and was refined as an idealized disordered methyl group.
details are summarized in Table 2Structural data
CCDC reference: 1831435
https://doi.org/10.1107/S2414314618004649/tk4048sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618004649/tk4048Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314618004649/tk4048Isup3.cdx
Data collection: APEX2 (Bruker, 2004); cell
APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2018/1 (Sheldrick, 2015b), PLATON (Spek, 2009) and publCIF (Westrip, 2010).C14H13NO | F(000) = 448 |
Mr = 211.25 | Dx = 1.259 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 4.6976 (4) Å | Cell parameters from 4170 reflections |
b = 19.3656 (18) Å | θ = 2.7–25.3° |
c = 12.3116 (12) Å | µ = 0.08 mm−1 |
β = 95.831 (3)° | T = 296 K |
V = 1114.21 (18) Å3 | Needle, orange |
Z = 4 | 0.15 × 0.10 × 0.10 mm |
Bruker Kappa APEXII CCD diffractometer | 2825 independent reflections |
Radiation source: fine-focus sealed tube | 1527 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ω and φ scan | θmax = 28.6°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −5→6 |
Tmin = 0.699, Tmax = 0.746 | k = −25→26 |
20153 measured reflections | l = −16→16 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.169 | w = 1/[σ2(Fo2) + (0.0565P)2 + 0.5019P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2825 reflections | Δρmax = 0.21 e Å−3 |
149 parameters | Δρmin = −0.18 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. The carbon-bound H-atoms were placed in calculated positions (C—H = 0.93–0.96 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2–1.5Uequiv(C)·The OH H atom was located in a difference Fourier map and refined freely. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.1821 (4) | 0.78020 (11) | 0.18545 (16) | 0.0421 (5) | |
C2 | 0.2951 (4) | 0.77295 (10) | 0.29511 (15) | 0.0373 (4) | |
C3 | 0.1864 (4) | 0.81482 (11) | 0.37342 (16) | 0.0430 (5) | |
H3 | 0.259387 | 0.809976 | 0.446105 | 0.052* | |
C4 | −0.0255 (4) | 0.86316 (11) | 0.34711 (18) | 0.0464 (5) | |
C5 | −0.1323 (5) | 0.86888 (11) | 0.23773 (18) | 0.0502 (6) | |
H5 | −0.274657 | 0.901142 | 0.217726 | 0.060* | |
C6 | −0.0319 (5) | 0.82791 (12) | 0.15850 (17) | 0.0505 (6) | |
H6 | −0.109020 | 0.832407 | 0.086232 | 0.061* | |
C7 | 0.5179 (4) | 0.72355 (10) | 0.32756 (16) | 0.0405 (5) | |
H7 | 0.589870 | 0.721013 | 0.400660 | 0.049* | |
C8 | 0.8311 (4) | 0.63294 (10) | 0.29122 (16) | 0.0401 (5) | |
C9 | 0.9307 (5) | 0.61802 (12) | 0.39877 (19) | 0.0533 (6) | |
H9 | 0.861945 | 0.642702 | 0.455421 | 0.064* | |
C10 | 1.1313 (5) | 0.56665 (13) | 0.4217 (2) | 0.0625 (7) | |
H10 | 1.196216 | 0.556890 | 0.493922 | 0.075* | |
C11 | 1.2361 (5) | 0.52984 (12) | 0.3395 (2) | 0.0653 (7) | |
H11 | 1.370708 | 0.495170 | 0.355807 | 0.078* | |
C12 | 1.1409 (5) | 0.54455 (13) | 0.2330 (2) | 0.0663 (7) | |
H12 | 1.211556 | 0.519957 | 0.176631 | 0.080* | |
C13 | 0.9401 (5) | 0.59586 (12) | 0.20938 (19) | 0.0531 (6) | |
H13 | 0.877201 | 0.605578 | 0.136922 | 0.064* | |
C14 | −0.1393 (6) | 0.90787 (13) | 0.4329 (2) | 0.0651 (7) | |
H14A | −0.284475 | 0.938039 | 0.399146 | 0.098* | 0.5 |
H14B | −0.219813 | 0.879186 | 0.485566 | 0.098* | 0.5 |
H14C | 0.013807 | 0.934903 | 0.468760 | 0.098* | 0.5 |
H14D | −0.042513 | 0.896713 | 0.503169 | 0.098* | 0.5 |
H14E | −0.107174 | 0.955566 | 0.416749 | 0.098* | 0.5 |
H14F | −0.340794 | 0.899849 | 0.433555 | 0.098* | 0.5 |
N1 | 0.6195 (3) | 0.68309 (9) | 0.25867 (13) | 0.0416 (4) | |
O1 | 0.2776 (4) | 0.74103 (9) | 0.10554 (12) | 0.0595 (5) | |
H1 | 0.427 (7) | 0.7120 (16) | 0.140 (2) | 0.097 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0427 (11) | 0.0475 (12) | 0.0359 (10) | −0.0030 (9) | 0.0028 (8) | 0.0041 (9) |
C2 | 0.0344 (10) | 0.0393 (10) | 0.0378 (10) | −0.0050 (8) | 0.0014 (8) | 0.0039 (8) |
C3 | 0.0439 (11) | 0.0464 (12) | 0.0380 (10) | −0.0040 (9) | 0.0001 (9) | 0.0013 (9) |
C4 | 0.0466 (12) | 0.0415 (11) | 0.0514 (12) | −0.0039 (9) | 0.0068 (10) | 0.0010 (10) |
C5 | 0.0463 (12) | 0.0465 (12) | 0.0571 (14) | 0.0035 (10) | 0.0021 (10) | 0.0115 (10) |
C6 | 0.0524 (13) | 0.0573 (14) | 0.0404 (11) | 0.0031 (11) | −0.0018 (10) | 0.0109 (10) |
C7 | 0.0382 (11) | 0.0460 (11) | 0.0363 (10) | −0.0038 (9) | −0.0014 (8) | 0.0024 (9) |
C8 | 0.0343 (10) | 0.0413 (11) | 0.0444 (11) | −0.0045 (8) | 0.0024 (8) | 0.0006 (9) |
C9 | 0.0559 (14) | 0.0532 (13) | 0.0497 (13) | 0.0078 (11) | −0.0004 (10) | 0.0013 (11) |
C10 | 0.0654 (16) | 0.0539 (14) | 0.0649 (16) | 0.0053 (12) | −0.0097 (12) | 0.0062 (12) |
C11 | 0.0550 (15) | 0.0471 (14) | 0.091 (2) | 0.0068 (11) | −0.0067 (14) | −0.0006 (13) |
C12 | 0.0588 (16) | 0.0605 (16) | 0.0800 (19) | 0.0094 (12) | 0.0097 (13) | −0.0170 (14) |
C13 | 0.0510 (13) | 0.0597 (14) | 0.0481 (12) | 0.0016 (11) | 0.0029 (10) | −0.0057 (11) |
C14 | 0.0708 (17) | 0.0554 (15) | 0.0692 (17) | 0.0098 (12) | 0.0074 (13) | −0.0064 (12) |
N1 | 0.0392 (9) | 0.0450 (10) | 0.0400 (9) | −0.0004 (8) | 0.0014 (7) | 0.0012 (8) |
O1 | 0.0679 (11) | 0.0728 (11) | 0.0370 (8) | 0.0156 (9) | 0.0008 (7) | −0.0007 (8) |
C1—O1 | 1.355 (2) | C9—C10 | 1.380 (3) |
C1—C6 | 1.381 (3) | C9—H9 | 0.9300 |
C1—C2 | 1.407 (3) | C10—C11 | 1.369 (3) |
C2—C3 | 1.396 (3) | C10—H10 | 0.9300 |
C2—C7 | 1.444 (3) | C11—C12 | 1.372 (4) |
C3—C4 | 1.381 (3) | C11—H11 | 0.9300 |
C3—H3 | 0.9300 | C12—C13 | 1.380 (3) |
C4—C5 | 1.393 (3) | C12—H12 | 0.9300 |
C4—C14 | 1.505 (3) | C13—H13 | 0.9300 |
C5—C6 | 1.377 (3) | C14—H14A | 0.9600 |
C5—H5 | 0.9300 | C14—H14B | 0.9600 |
C6—H6 | 0.9300 | C14—H14C | 0.9600 |
C7—N1 | 1.282 (2) | C14—H14D | 0.9600 |
C7—H7 | 0.9300 | C14—H14E | 0.9600 |
C8—C13 | 1.377 (3) | C14—H14F | 0.9600 |
C8—C9 | 1.389 (3) | O1—H1 | 0.96 (3) |
C8—N1 | 1.418 (2) | ||
O1—C1—C6 | 119.16 (18) | C10—C9—H9 | 119.9 |
O1—C1—C2 | 121.36 (18) | C8—C9—H9 | 119.9 |
C6—C1—C2 | 119.48 (19) | C11—C10—C9 | 120.9 (2) |
C3—C2—C1 | 118.42 (18) | C11—C10—H10 | 119.5 |
C3—C2—C7 | 119.98 (17) | C9—C10—H10 | 119.5 |
C1—C2—C7 | 121.61 (18) | C10—C11—C12 | 119.4 (2) |
C4—C3—C2 | 122.52 (19) | C10—C11—H11 | 120.3 |
C4—C3—H3 | 118.7 | C12—C11—H11 | 120.3 |
C2—C3—H3 | 118.7 | C11—C12—C13 | 120.0 (2) |
C3—C4—C5 | 117.4 (2) | C11—C12—H12 | 120.0 |
C3—C4—C14 | 121.6 (2) | C13—C12—H12 | 120.0 |
C5—C4—C14 | 120.9 (2) | C8—C13—C12 | 121.2 (2) |
C6—C5—C4 | 121.6 (2) | C8—C13—H13 | 119.4 |
C6—C5—H5 | 119.2 | C12—C13—H13 | 119.4 |
C4—C5—H5 | 119.2 | C4—C14—H14A | 109.5 |
C5—C6—C1 | 120.6 (2) | C4—C14—H14B | 109.5 |
C5—C6—H6 | 119.7 | H14A—C14—H14B | 109.5 |
C1—C6—H6 | 119.7 | C4—C14—H14C | 109.5 |
N1—C7—C2 | 122.01 (18) | H14A—C14—H14C | 109.5 |
N1—C7—H7 | 119.0 | H14B—C14—H14C | 109.5 |
C2—C7—H7 | 119.0 | H14D—C14—H14E | 109.5 |
C13—C8—C9 | 118.3 (2) | H14D—C14—H14F | 109.5 |
C13—C8—N1 | 116.88 (18) | H14E—C14—H14F | 109.5 |
C9—C8—N1 | 124.77 (19) | C7—N1—C8 | 121.95 (17) |
C10—C9—C8 | 120.1 (2) | C1—O1—H1 | 106.9 (18) |
O1—C1—C2—C3 | −179.81 (18) | C3—C2—C7—N1 | 178.48 (18) |
C6—C1—C2—C3 | −0.2 (3) | C1—C2—C7—N1 | −1.4 (3) |
O1—C1—C2—C7 | 0.0 (3) | C13—C8—C9—C10 | −0.7 (3) |
C6—C1—C2—C7 | 179.64 (19) | N1—C8—C9—C10 | 178.0 (2) |
C1—C2—C3—C4 | −0.5 (3) | C8—C9—C10—C11 | 0.2 (4) |
C7—C2—C3—C4 | 179.67 (18) | C9—C10—C11—C12 | 0.3 (4) |
C2—C3—C4—C5 | 0.5 (3) | C10—C11—C12—C13 | −0.3 (4) |
C2—C3—C4—C14 | −179.9 (2) | C9—C8—C13—C12 | 0.7 (3) |
C3—C4—C5—C6 | 0.2 (3) | N1—C8—C13—C12 | −178.1 (2) |
C14—C4—C5—C6 | −179.4 (2) | C11—C12—C13—C8 | −0.2 (4) |
C4—C5—C6—C1 | −0.9 (3) | C2—C7—N1—C8 | −177.73 (17) |
O1—C1—C6—C5 | −179.5 (2) | C13—C8—N1—C7 | −175.27 (19) |
C2—C1—C6—C5 | 0.9 (3) | C9—C8—N1—C7 | 6.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.96 (3) | 1.73 (3) | 2.603 (2) | 148 (3) |
Acknowledgements
The authors are grateful to the Sophisticated Analytical Instrument Facility (SAIF), IITM, Chennai, Tamilnadu, India, for the single-crystal X-ray diffraction data.
References
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