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Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): o287.
Published online 2010 January 9. doi:  10.1107/S1600536809055573
PMCID: PMC2979675

(E)-2-[(2-Ethyl­phen­yl)imino­meth­yl]-6-methoxy­phenol

Abstract

The mol­ecule of the title compound, C16H17NO2, adopts the phenol–imine tautomeric form with a strong intra­molecular O—H(...)N hydrogen bond and an E conformation with respect to the azomethine C=N bond. The dihedral angle between the aromatic rings is 21.23 (9)°. The ethyl group is disordered over two orientations with occupancies of 0.598 (6) and 0.402 (6). In the crystal, the mol­ecules are linked into chains along the b axis by C—H(...)π inter­actions.

Related literature

For general background to o-hydr­oxy Schiff bases, see: Stewart & Lingafelter (1959 [triangle]); Calligaris et al. (1972 [triangle]); Maslen & Waters (1975 [triangle]). For the photochromic and thermochromic characteristics of Schiff base compounds, see: Cohen et al. (1964 [triangle]); Moustakali-Mavridis et al. (1980 [triangle]); Hadjoudis et al. (1987 [triangle]); Xu et al. (1994 [triangle]). For a related structure, see: Yüce et al. (2004 [triangle]).

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Object name is e-66-0o287-scheme1.jpg

Experimental

Crystal data

  • C16H17NO2
  • M r = 255.31
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o287-efi1.jpg
  • a = 18.2379 (7) Å
  • b = 5.2044 (2) Å
  • c = 15.0950 (7) Å
  • β = 113.788 (3)°
  • V = 1311.05 (9) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 150 K
  • 0.58 × 0.39 × 0.08 mm

Data collection

  • Stoe IPDS II diffractometer
  • Absorption correction: integration (X-RED32; Stoe & Cie, 2002 [triangle]) T min = 0.961, T max = 0.993
  • 18335 measured reflections
  • 3014 independent reflections
  • 2353 reflections with I > 2σ(I)
  • R int = 0.072

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.115
  • S = 1.03
  • 3014 reflections
  • 196 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.32 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 [triangle]); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809055573/ci5005sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809055573/ci5005Isup2.hkl

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

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant No. F279 of the University Research Fund).

supplementary crystallographic information

Comment

o-Hydroxy Schiff bases derived from the reaction of o-hydroxyaldehydes with aniline have been examined extensively (Steward & Lingafelter, 1959; Calligaris et al., 1972; Maslen & Waters, 1975). Schiff base compounds display interesting photochromic and thermochromic features and can be classified in terms of these (Cohen et al., 1964; Moustakali-Mavridis et al., 1980; Hadjoudis et al., 1987). Photo- and thermochromism arise via H atom transfer from the hydroxy O atom to the N atom (Hadjoudis et al., 1987; Xu et al., 1994).

The molecule of the title compound (Fig. 1) exists in the phenol-imine form which is confirmed by C13—O1 and C7—N1 bond distances. These distances agree with the corresponding distances in 1-{4-[(2-hydroxybenzylidene)amino]phenyl}ethanone, a related structure [C—O = 1.3500 (17) and C—N = 1.2772 (16) Å; Yüce et al., 2004].

The title molecule is not planar; the dihedral angle between the two benzene rings is 21.23 (9)°. An intramolecular O1—H1···N1 hydrogen bond (Fig. 1) generates an S(6) ring-motif.

The crystal structure is stabilized by weak C—H···π interactions involving H14C and C8–C13 ring (Fig. 2).

Experimental

A solution of 3-methoxysalicylaldehyde (0.5 g 3.3 mmol) in ethanol (20 ml) was added to a solution of 2-ethylaniline (0.4 g 3.3 mmol) in ethanol (20 ml). The reaction mixture was stirred for 1 h under reflux. Single crystals of the title compound were obtained by slow evaporation of an ethanol solution (yield 72%, m.p. 339-340 K).

Refinement

The ethyl group is disordered over two orientations with occupancies of 0.598 (6) and 0.402 (6). Atom H1 was located in a difference map and refined freely. The remaining H atoms were placed in calculated positions and constrained to ride on their parents atoms, with C-H = 0.93–0.96 Å and Uiso(H) = 1.2Ueq(C) and 1.5Ueq(Cmethyl).

Figures

Fig. 1.
The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates a hydrogen bond. Only the major disorder component is shown.
Fig. 2.
A partial packing diagram of the title compound. Dashed lines indicate C—H···π interactions.

Crystal data

C16H17NO2F(000) = 544
Mr = 255.31Dx = 1.293 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2353 reflections
a = 18.2379 (7) Åθ = 1.5–28.0°
b = 5.2044 (2) ŵ = 0.09 mm1
c = 15.0950 (7) ÅT = 150 K
β = 113.788 (3)°Plate, brown
V = 1311.05 (9) Å30.58 × 0.39 × 0.08 mm
Z = 4

Data collection

Stoe IPDS II diffractometer3014 independent reflections
Radiation source: fine-focus sealed tube2353 reflections with I > 2σ(I)
graphiteRint = 0.072
Detector resolution: 6.67 pixels mm-1θmax = 27.6°, θmin = 2.4°
ω scanh = −23→23
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)k = −6→6
Tmin = 0.961, Tmax = 0.993l = −19→19
18335 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.115w = 1/[σ2(Fo2) + (0.052P)2 + 0.279P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
3014 reflectionsΔρmax = 0.26 e Å3
196 parametersΔρmin = −0.32 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.024 (3)

Special details

Experimental. 320 frames, detector distance = 100 mm
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*/UeqOcc. (<1)
C16A0.0701 (3)0.3212 (10)0.5111 (3)0.0532 (15)0.402 (6)
H16A0.06280.34250.57020.080*0.402 (6)
H16B0.01880.30270.45810.080*0.402 (6)
H16C0.09700.46910.50060.080*0.402 (6)
C15A0.1206 (3)0.0813 (10)0.5183 (4)0.0411 (12)0.402 (6)
H15A0.0944−0.07270.52740.049*0.402 (6)
H15B0.17340.09530.57050.049*0.402 (6)
C15B0.09657 (17)0.2040 (7)0.4866 (2)0.0380 (9)0.598 (6)
H15C0.11140.38390.49670.046*0.598 (6)
H15D0.03880.19030.46390.046*0.598 (6)
C16B0.13777 (19)0.0531 (6)0.5796 (3)0.0470 (9)0.598 (6)
H16D0.12200.12020.62850.070*0.598 (6)
H16E0.19480.06810.60090.070*0.598 (6)
H16F0.1226−0.12440.56820.070*0.598 (6)
H10.2630 (14)0.462 (4)0.5862 (17)0.077 (7)*
O10.29046 (6)0.5645 (2)0.64484 (7)0.0387 (3)
N10.23740 (7)0.3745 (3)0.47070 (8)0.0376 (3)
C120.38182 (8)0.9118 (3)0.68144 (9)0.0314 (3)
O20.37858 (6)0.9107 (2)0.77070 (7)0.0386 (3)
C90.38032 (8)0.8881 (3)0.49637 (10)0.0344 (3)
H90.37980.88120.43450.041*
C130.33418 (7)0.7266 (3)0.61589 (9)0.0306 (3)
C80.33213 (7)0.7187 (3)0.52183 (9)0.0315 (3)
C140.42206 (9)1.1110 (3)0.83509 (10)0.0406 (3)
H14A0.41621.09390.89520.061*
H14B0.40151.27470.80660.061*
H14C0.47771.09890.84680.061*
C110.42846 (8)1.0776 (3)0.65443 (10)0.0338 (3)
H110.46021.19930.69820.041*
C70.27988 (8)0.5403 (3)0.45018 (10)0.0346 (3)
H70.27720.54680.38740.042*
C20.20659 (9)0.1179 (3)0.32266 (10)0.0407 (3)
H20.24930.19250.31330.049*
C100.42817 (8)1.0634 (3)0.56190 (10)0.0347 (3)
H100.46051.17320.54470.042*
C30.16088 (10)−0.0684 (3)0.25904 (11)0.0474 (4)
H30.1729−0.11860.20730.057*
C10.18945 (8)0.1950 (3)0.40048 (10)0.0378 (3)
C40.09745 (10)−0.1796 (3)0.27231 (11)0.0479 (4)
H40.0666−0.30530.22980.057*
C60.12496 (10)0.0848 (4)0.41384 (13)0.0594 (5)
C50.08014 (10)−0.1034 (4)0.34882 (13)0.0568 (5)
H50.0373−0.17940.35750.068*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C16A0.049 (2)0.056 (3)0.061 (3)0.001 (2)0.028 (2)−0.013 (2)
C15A0.041 (2)0.041 (3)0.043 (4)−0.007 (2)0.019 (2)0.004 (2)
C15B0.0310 (13)0.0355 (19)0.0482 (16)0.0008 (13)0.0168 (12)0.0063 (14)
C16B0.0583 (17)0.0449 (16)0.042 (2)−0.0002 (13)0.0248 (15)0.0062 (13)
O10.0388 (5)0.0449 (6)0.0382 (5)−0.0100 (5)0.0216 (4)−0.0055 (5)
N10.0279 (5)0.0472 (7)0.0369 (6)−0.0015 (5)0.0124 (5)−0.0066 (5)
C120.0324 (6)0.0346 (7)0.0296 (6)0.0033 (6)0.0151 (5)0.0015 (5)
O20.0447 (5)0.0440 (6)0.0327 (5)−0.0101 (5)0.0214 (4)−0.0068 (4)
C90.0384 (7)0.0358 (7)0.0318 (6)0.0057 (6)0.0169 (6)0.0043 (5)
C130.0271 (6)0.0332 (7)0.0338 (6)0.0025 (5)0.0146 (5)0.0020 (5)
C80.0290 (6)0.0337 (7)0.0315 (6)0.0053 (5)0.0117 (5)0.0016 (5)
C140.0491 (8)0.0413 (9)0.0362 (7)−0.0070 (7)0.0220 (6)−0.0083 (6)
C110.0358 (7)0.0316 (7)0.0345 (7)−0.0002 (6)0.0148 (6)0.0000 (6)
C70.0307 (6)0.0404 (8)0.0318 (6)0.0055 (6)0.0116 (5)−0.0002 (6)
C20.0402 (7)0.0450 (9)0.0350 (7)−0.0007 (6)0.0132 (6)−0.0004 (6)
C100.0381 (7)0.0329 (7)0.0372 (7)0.0013 (6)0.0193 (6)0.0050 (6)
C30.0531 (9)0.0507 (10)0.0350 (7)−0.0020 (8)0.0143 (7)−0.0054 (7)
C10.0299 (6)0.0454 (9)0.0340 (7)−0.0001 (6)0.0088 (5)−0.0047 (6)
C40.0426 (8)0.0488 (9)0.0396 (8)−0.0027 (7)0.0035 (6)−0.0058 (7)
C60.0407 (8)0.0860 (14)0.0566 (10)−0.0213 (9)0.0248 (8)−0.0273 (10)
C50.0376 (8)0.0732 (13)0.0584 (10)−0.0174 (8)0.0180 (8)−0.0171 (9)

Geometric parameters (Å, °)

C16A—C15A1.529 (7)C9—C101.370 (2)
C16A—H16A0.96C9—C81.4035 (19)
C16A—H16B0.96C9—H90.93
C16A—H16C0.96C13—C81.4058 (17)
C15A—C61.611 (5)C8—C71.4521 (19)
C15A—H15A0.97C14—H14A0.96
C15A—H15B0.97C14—H14B0.96
C15B—C16B1.516 (5)C14—H14C0.96
C15B—C61.523 (3)C11—C101.3966 (18)
C15B—H15C0.97C11—H110.93
C15B—H15D0.97C7—H70.93
C16B—H16D0.96C2—C31.382 (2)
C16B—H16E0.96C2—C11.391 (2)
C16B—H16F0.96C2—H20.93
O1—C131.3490 (16)C10—H100.93
O1—H10.98 (2)C3—C41.378 (2)
N1—C71.2781 (19)C3—H30.93
N1—C11.4193 (18)C1—C61.394 (2)
C12—O21.3722 (15)C4—C51.373 (2)
C12—C111.3834 (19)C4—H40.93
C12—C131.4034 (19)C6—C51.394 (2)
O2—C141.4274 (17)C5—H50.93
C15A—C16A—H16A109.5C9—C8—C7119.54 (12)
C15A—C16A—H16B109.5C13—C8—C7120.87 (12)
H16A—C16A—H16B109.5O2—C14—H14A109.5
C15A—C16A—H16C109.5O2—C14—H14B109.5
H16A—C16A—H16C109.5H14A—C14—H14B109.5
H16B—C16A—H16C109.5O2—C14—H14C109.5
C16A—C15A—C6100.8 (4)H14A—C14—H14C109.5
C16A—C15A—H15A111.6H14B—C14—H14C109.5
C6—C15A—H15A111.6C12—C11—C10120.47 (13)
C16A—C15A—H15B111.6C12—C11—H11119.8
C6—C15A—H15B111.6C10—C11—H11119.8
H15A—C15A—H15B109.4N1—C7—C8122.06 (12)
C16B—C15B—C6105.7 (3)N1—C7—H7119.0
C16B—C15B—H15C110.6C8—C7—H7119.0
C6—C15B—H15C110.6C3—C2—C1120.71 (14)
C16B—C15B—H15D110.6C3—C2—H2119.6
C6—C15B—H15D110.6C1—C2—H2119.6
H15C—C15B—H15D108.7C9—C10—C11120.11 (13)
C15B—C16B—H16D109.5C9—C10—H10119.9
C15B—C16B—H16E109.5C11—C10—H10119.9
H16D—C16B—H16E109.5C4—C3—C2120.00 (14)
C15B—C16B—H16F109.5C4—C3—H3120.0
H16D—C16B—H16F109.5C2—C3—H3120.0
H16E—C16B—H16F109.5C2—C1—C6119.58 (14)
C13—O1—H1101.6 (13)C2—C1—N1122.67 (13)
C7—N1—C1120.97 (12)C6—C1—N1117.68 (13)
O2—C12—C11124.55 (12)C5—C4—C3119.48 (15)
O2—C12—C13115.46 (11)C5—C4—H4120.3
C11—C12—C13119.99 (12)C3—C4—H4120.3
C12—O2—C14115.69 (10)C5—C6—C1118.45 (15)
C10—C9—C8120.50 (12)C5—C6—C15B121.37 (16)
C10—C9—H9119.7C1—C6—C15B119.27 (17)
C8—C9—H9119.7C5—C6—C15A115.8 (2)
O1—C13—C12118.68 (11)C1—C6—C15A121.60 (19)
O1—C13—C8122.03 (12)C4—C5—C6121.78 (16)
C12—C13—C8119.27 (12)C4—C5—H5119.1
C9—C8—C13119.58 (12)C6—C5—H5119.1
C11—C12—O2—C145.35 (19)C3—C2—C1—N1176.31 (14)
C13—C12—O2—C14−175.41 (12)C7—N1—C1—C225.3 (2)
O2—C12—C13—O1−0.49 (18)C7—N1—C1—C6−157.73 (16)
C11—C12—C13—O1178.79 (12)C2—C3—C4—C50.2 (3)
O2—C12—C13—C8178.24 (11)C2—C1—C6—C50.9 (3)
C11—C12—C13—C8−2.48 (19)N1—C1—C6—C5−176.19 (17)
C10—C9—C8—C13−1.1 (2)C2—C1—C6—C15B−168.4 (2)
C10—C9—C8—C7177.95 (13)N1—C1—C6—C15B14.5 (3)
O1—C13—C8—C9−178.51 (12)C2—C1—C6—C15A156.9 (3)
C12—C13—C8—C92.80 (19)N1—C1—C6—C15A−20.1 (4)
O1—C13—C8—C72.45 (19)C16B—C15B—C6—C595.4 (3)
C12—C13—C8—C7−176.23 (12)C16B—C15B—C6—C1−95.6 (3)
O2—C12—C11—C10179.66 (13)C16B—C15B—C6—C15A7.7 (3)
C13—C12—C11—C100.4 (2)C16A—C15A—C6—C5−108.3 (3)
C1—N1—C7—C8−177.25 (12)C16A—C15A—C6—C195.1 (3)
C9—C8—C7—N1176.91 (13)C16A—C15A—C6—C15B0.4 (3)
C13—C8—C7—N1−4.1 (2)C3—C4—C5—C60.1 (3)
C8—C9—C10—C11−1.0 (2)C1—C6—C5—C4−0.7 (3)
C12—C11—C10—C91.3 (2)C15B—C6—C5—C4168.4 (2)
C1—C2—C3—C40.1 (3)C15A—C6—C5—C4−158.1 (3)
C3—C2—C1—C6−0.6 (3)

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C8–C13 ring.
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.98 (2)1.68 (2)2.6023 (15)156 (2)
C14—H14c···Cg1i0.962.833.6241 (18)141

Symmetry codes: (i) −x+1, y+1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI5005).

References

  • Calligaris, M., Nardin, G. & Randaccio, L. (1972). Coord. Chem. Rev.7, 385–403.
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  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Hadjoudis, E., Vitterakis, M. & Maviridis, I. M. (1987). Tetrahedron, 43, 1345–1360.
  • Maslen, H. S. & Waters, T. N. (1975). Coord. Chem. Rev.17, 137–176.
  • Moustakali-Mavridis, I., Hadjoudis, B. & Mavridis, A. (1980). Acta Cryst. B36, 1126–1130.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Stewart, J. M. & Lingafelter, E. C. (1959). Acta Cryst.12, 842–845.
  • Stoe & Cie (2002). X-AREA and X-RED Stoe & Cie, Darmstadt, Germany.
  • Xu, X.-X., You, X.-Z., Sun, Z.-F., Wang, X. & Liu, H.-X. (1994). Acta Cryst. C50, 1169–1171.
  • Yüce, S., Özek, A., Albayrak, Ç., Odabaşoğlu, M. & Büyükgüngör, O. (2004). Acta Cryst. E60, o718–o719.

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