6-Meth­oxy-2-[(E)-phenyl­imino­meth­yl]phenol

Abstract

The title compound, C₁₄H₁₃NO₂, was obtained by the condensation reaction of o-vanillin and aniline in ethanol. The mol­ecule adopts the phenol–imine tautomeric form and an E conformation with respect to the azomethine C=N bond. The dihedral angle between the aromatic rings is 30.57 (10)°. In the crystal, mol­ecules are linked by inter­molecular C—H⋯O hydrogen bonds into zigzag chains parallel to the b axis.

Related literature

For related metal complexes with Schiff base ligands derived from o-vanillin and aniline, see: Li et al. (2008 ▶); Liu et al. (2009 ▶); Xian et al. (2008 ▶); Zhao et al. (2007 ▶). For the syntheses and anti­bacterial activities of rare earth complexes with Schiff base ligands derived from o-vanillin and adamantane­amine, see: Zhao et al. (2005 ▶).

Experimental

Crystal data

• C₁₄H₁₃NO₂

• M _r = 227.25

• Orthorhombic,

• a = 6.0882 (4) Å

• b = 9.1862 (5) Å

• c = 21.0800 (12) Å

• V = 1178.95 (12) ų

• Z = 4

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 296 K

• 0.33 × 0.22 × 0.18 mm

Data collection

• Bruker APEXII area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T _min = 0.978, T _max = 0.985

• 11856 measured reflections

• 1190 independent reflections

• 1007 reflections with I > 2σ(I)

• R _int = 0.081

Refinement

• R[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 0.140

• S = 1.02

• 1190 reflections

• 154 parameters

• H-atom parameters constrained

• Δρ_max = 0.19 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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
C9—H9A⋯O1i	0.93	2.57	3.485 (4)	168

Symmetry code: (i) .

supplementary crystallographic information

Comment

For many years, there has been considerable interest in the study of Schiff base compounds due to their biological activity (Zhao et al., 2005). Recently, we have reported the crystal structure of some Schiff bases metal complexes (Zhao et al., 2007; Xian et al. 2008; Li et al. 2008; Liu et al. 2009). As an extention of our work in the structural characterization of Schiff base compounds, we synthesized the title compound and report its crystal structure herein.

In the molecule of the title compound (Fig. 1), the C—O bond lengths range from 1.350 (4) to 1.419 (4) Å. The C—N and C═N bond lengths are 1.428 (3) and 1.285 (4) Å, respectively. The molecule is not planar, with the dihedral angle between the two aromatic rings of 30.57 (10)°. In the crystal structure (Fig. 2), intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into chains parallel to the b axis.

Experimental

Reagents and solvents used were of commercially available quality and were not purified before using. A mixture of o-vanillin (0.152 g, 1.0 mmol) and aniline (0.093 g, 1.0 mmol) in absolute ethanol (30 ml) was stirred and refluxed for 4 h. The solution was then cooled to room temperature. Orange single crystals suitable for X-ray diffraction were obtained by slow evaporation of the solvent after about 5 d.

Refinement

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.96 Å, O—H = 0.82 Å, and with U_iso(H) = 1.2U_eq(C, O) or 1.5U_eq(C) for methyl H atoms. In the absence of significant anomalous scattering effects, 820 Friedel pairs were averaged in the final refinement.

Figures

Fig. 1.

The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 2.

Packing diagram of the title compound compound viewed approximately along the a axis. Intermolecular hydrogen bonds are drawn as dashed lines.

Crystal data

C14H13NO2	F(000) = 480
Mr = 227.25	Dx = 1.280 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5745 reflections
a = 6.0882 (4) Å	θ = 2.4–25.0°
b = 9.1862 (5) Å	µ = 0.09 mm−1
c = 21.0800 (12) Å	T = 296 K
V = 1178.95 (12) Å3	Block, orange
Z = 4	0.33 × 0.22 × 0.18 mm

Data collection

Bruker APEXII area-detector diffractometer	1190 independent reflections
Radiation source: fine-focus sealed tube	1007 reflections with I > 2σ(I)
graphite	Rint = 0.081
φ and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −7→7
Tmin = 0.978, Tmax = 0.985	k = −10→10
11856 measured reflections	l = −25→23

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0787P)2 + 0.4631P] where P = (Fo2 + 2Fc2)/3
1190 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Special details

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. 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.1467 (5)	0.8849 (3)	0.19232 (12)	0.0471 (6)
O2	−0.0125 (4)	1.0344 (2)	0.09751 (11)	0.0546 (6)
H2B	0.1106	0.9995	0.1017	0.066*
C6	−0.1608 (5)	0.9260 (3)	0.09144 (13)	0.0425 (7)
O1	−0.3287 (4)	1.0709 (2)	0.01403 (10)	0.0539 (6)
C1	−0.1531 (6)	0.7999 (3)	0.12880 (14)	0.0466 (7)
C5	−0.3315 (6)	0.9420 (3)	0.04705 (14)	0.0454 (7)
C7	0.2914 (5)	0.8685 (3)	0.24514 (15)	0.0456 (7)
C10	0.5867 (6)	0.8458 (5)	0.34404 (19)	0.0637 (10)
H10A	0.6870	0.8378	0.3771	0.076*
C4	−0.4870 (6)	0.8348 (4)	0.03963 (15)	0.0537 (8)
H4A	−0.5999	0.8468	0.0104	0.064*
C12	0.0067 (6)	0.7846 (4)	0.17918 (15)	0.0496 (8)
H12A	0.0082	0.6993	0.2029	0.060*
C2	−0.3120 (6)	0.6922 (4)	0.12031 (15)	0.0551 (9)
H2A	−0.3069	0.6085	0.1451	0.066*
C8	0.2343 (6)	0.7914 (4)	0.30001 (15)	0.0510 (8)
H8A	0.0970	0.7477	0.3034	0.061*
C13	0.4930 (7)	0.9357 (4)	0.24102 (17)	0.0548 (8)
H13A	0.5290	0.9899	0.2052	0.066*
C3	−0.4755 (7)	0.7075 (4)	0.07616 (16)	0.0581 (9)
H3A	−0.5783	0.6338	0.0704	0.070*
C14	−0.5226 (7)	1.1074 (5)	−0.0198 (2)	0.0693 (11)
H14A	−0.5026	1.1992	−0.0408	0.104*
H14B	−0.6436	1.1144	0.0093	0.104*
H14C	−0.5530	1.0333	−0.0507	0.104*
C9	0.3840 (6)	0.7807 (4)	0.34918 (17)	0.0578 (9)
H9A	0.3475	0.7295	0.3858	0.069*
C11	0.6421 (6)	0.9225 (4)	0.29039 (19)	0.0647 (10)
H11A	0.7798	0.9655	0.2872	0.078*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0523 (14)	0.0443 (13)	0.0446 (14)	0.0027 (14)	0.0003 (13)	0.0060 (11)
O2	0.0561 (13)	0.0449 (13)	0.0629 (14)	−0.0041 (12)	−0.0041 (12)	0.0090 (10)
C6	0.0494 (16)	0.0359 (15)	0.0422 (15)	0.0024 (16)	0.0047 (14)	0.0004 (12)
O1	0.0657 (14)	0.0443 (12)	0.0516 (12)	0.0015 (13)	−0.0101 (12)	0.0121 (10)
C1	0.0581 (18)	0.0405 (16)	0.0413 (15)	0.0056 (17)	0.0016 (15)	0.0024 (13)
C5	0.0549 (17)	0.0401 (16)	0.0413 (15)	0.0055 (16)	0.0021 (15)	0.0010 (13)
C7	0.0501 (16)	0.0387 (16)	0.0479 (17)	0.0054 (15)	0.0012 (14)	0.0004 (13)
C10	0.060 (2)	0.063 (2)	0.068 (2)	0.007 (2)	−0.0147 (19)	−0.009 (2)
C4	0.0639 (19)	0.052 (2)	0.0455 (17)	−0.0025 (18)	−0.0020 (17)	0.0002 (14)
C12	0.0612 (19)	0.0403 (15)	0.0473 (17)	0.0064 (18)	0.0006 (16)	0.0073 (13)
C2	0.075 (2)	0.0416 (17)	0.0491 (17)	−0.008 (2)	−0.0019 (17)	0.0076 (14)
C8	0.0520 (17)	0.0504 (19)	0.0507 (17)	0.0016 (17)	0.0033 (15)	0.0051 (15)
C13	0.0557 (16)	0.0503 (18)	0.058 (2)	−0.0022 (19)	0.0103 (17)	0.0031 (16)
C3	0.066 (2)	0.0484 (18)	0.060 (2)	−0.0104 (19)	−0.0056 (18)	0.0030 (16)
C14	0.069 (2)	0.063 (2)	0.076 (2)	0.007 (2)	−0.014 (2)	0.022 (2)
C9	0.072 (2)	0.050 (2)	0.0511 (18)	0.007 (2)	−0.0057 (19)	0.0037 (15)
C11	0.0486 (18)	0.059 (2)	0.087 (3)	−0.0045 (19)	0.002 (2)	−0.009 (2)

Geometric parameters (Å, °)

N1—C12	1.285 (4)	C4—C3	1.402 (5)
N1—C7	1.428 (4)	C4—H4A	0.9300
O2—C6	1.350 (4)	C12—H12A	0.9300
O2—H2B	0.8200	C2—C3	1.370 (5)
C6—C1	1.401 (4)	C2—H2A	0.9300
C6—C5	1.406 (4)	C8—C9	1.384 (5)
O1—C5	1.374 (4)	C8—H8A	0.9300
O1—C14	1.419 (4)	C13—C11	1.386 (5)
C1—C2	1.396 (5)	C13—H13A	0.9300
C1—C12	1.447 (5)	C3—H3A	0.9300
C5—C4	1.375 (5)	C14—H14A	0.9600
C7—C13	1.377 (5)	C14—H14B	0.9600
C7—C8	1.400 (5)	C14—H14C	0.9600
C10—C11	1.374 (6)	C9—H9A	0.9300
C10—C9	1.375 (5)	C11—H11A	0.9300
C10—H10A	0.9300
C12—N1—C7	120.1 (3)	C3—C2—C1	121.2 (3)
C6—O2—H2B	109.5	C3—C2—H2A	119.4
O2—C6—C1	122.3 (3)	C1—C2—H2A	119.4
O2—C6—C5	118.7 (3)	C9—C8—C7	119.4 (3)
C1—C6—C5	119.0 (3)	C9—C8—H8A	120.3
C5—O1—C14	116.6 (3)	C7—C8—H8A	120.3
C2—C1—C6	119.4 (3)	C7—C13—C11	119.8 (3)
C2—C1—C12	119.4 (3)	C7—C13—H13A	120.1
C6—C1—C12	121.0 (3)	C11—C13—H13A	120.1
O1—C5—C4	124.6 (3)	C2—C3—C4	119.7 (3)
O1—C5—C6	114.7 (3)	C2—C3—H3A	120.1
C4—C5—C6	120.7 (3)	C4—C3—H3A	120.1
C13—C7—C8	120.0 (3)	O1—C14—H14A	109.5
C13—C7—N1	117.0 (3)	O1—C14—H14B	109.5
C8—C7—N1	123.0 (3)	H14A—C14—H14B	109.5
C11—C10—C9	120.5 (4)	O1—C14—H14C	109.5
C11—C10—H10A	119.7	H14A—C14—H14C	109.5
C9—C10—H10A	119.7	H14B—C14—H14C	109.5
C5—C4—C3	120.0 (3)	C10—C9—C8	120.1 (3)
C5—C4—H4A	120.0	C10—C9—H9A	120.0
C3—C4—H4A	120.0	C8—C9—H9A	120.0
N1—C12—C1	122.3 (3)	C10—C11—C13	120.2 (3)
N1—C12—H12A	118.8	C10—C11—H11A	119.9
C1—C12—H12A	118.8	C13—C11—H11A	119.9

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O1i	0.93	2.57	3.485 (4)	168

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