2-[(2-Meth­oxy­benzyl­idene)amino]­phenol

Aslam, M.; Anis, I.; Afza, N.; Hussain, M.T.; Yousuf, S.

doi:10.1107/S1600536812016224

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1447

doi:10.1107/S1600536812016224

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2-[(2-Methoxybenzylidene)amino]phenol

M. Aslam,^a,^b ‡ I. Anis,^b N. Afza,^a M. T. Hussain ^c and S. Yousuf ^d ^*

^aPharmaceutical Research Centre, PCSIR Laboratories Complex, Karachi, Pakistan and Department of Chemistry, University of Karachi, Karachi, Pakistan, ^bDepartment of Chemistry, University of Karachi, Karachi, Pakistan, ^cDepartment of Applied Sciences, National Textile University, Faisalabad 37610, Pakistan, and ^dH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan
^*Correspondence e-mail: dr.sammer.yousuf@gmail.com

(Received 23 March 2012; accepted 14 April 2012; online 21 April 2012)

In the title compound, C₁₄H₁₃NO₂, the azomethine double bond adopts an E conformation and the benzene rings form a dihedral angle of 77.70 (7)°. In the crystal, molecules are linked by O—H⋯N and C—H⋯O hydrogen bonds and arranged in a zigzag fashion, forming infinite chains parallel to the c axis, resulting in a graph-set R₂²(9) motif.

Related literature

For the biological activity of Schiff bases, see: Khan et al. (2009 ); Gerdemann et al. (2002 ); Samadhiya & Halve (2001 ). For a related structure, see: Liang et al. (2009 ). For graph-set motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₄H₁₃NO₂
M_r = 227.25
Monoclinic, P 2₁ /c
a = 9.8709 (5) Å
b = 6.6606 (3) Å
c = 18.6128 (9) Å
β = 105.249 (1)°
V = 1180.63 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 273 K
0.49 × 0.17 × 0.16 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.959, T_max = 0.986
6660 measured reflections
2186 independent reflections
1680 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.100
S = 1.04
2186 reflections
159 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯N1ⁱ	0.88 (2)	1.94 (2)	2.796 (2)	163 (2)
C10—H10A⋯O2ⁱ	0.93	2.56	3.269 (2)	133
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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: SHELXTL, PARST (Nardelli, 1995 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812016224/pv2528sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812016224/pv2528Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812016224/pv2528Isup3.cml

checkCIF report

Comment top

Schiff base ligands have remained an imperative part of research due to their used as intermediates and precursors for the synthesis of a variety of organic compounds having a broad range of biological activities (Khan et al., 2009; Gerdemann et al., 2002; Samadhiya & Halve, 2001). The title compound was prepared as a part of our ongoing research on bioactive compounds.

In the title molecule (Fig. 1), the azomethine (C═N, 1.2729 (18) Å) double bond adopts an E configuration. The bond lengths and angles in the title compound are similar to the corresponding bond lenghts and bond angles reported in a closely related compound, 2-(2,3,4-trimethoxy-6-methylbenzylideneamino)phenol (Liang et al., 2009). The crystal structure is stabilized by O2—H2A···N1 and C1—H1B···O1 intermolecular hydrogen bonds resulting in chains of molecules lying parallel to the c-axis in a zig zag fashion (Fig. 2 and Tab. 1). The molecules lying about screw axis parallel to the c-axis form 9-membered rings due to hydrogen bonds in a motif with graph set R₂²(9) (Bernstein et al., 1995).

Related literature top

For the biological activity of Schiff bases, see: Khan et al. (2009); Gerdemann et al. (2002); Samadhiya & Halve (2001). For a related structure, see: Liang et al. (2009). For graph-set motifs, see: Bernstein et al. (1995).

Experimental top

A mixture of 2-methoxybenzaldehyde (0.01 mol, 1.36 g) and 2-aminophenol (0.01 mol, 1.09 g) in ethanol (50 ml) along with 3–4 drops of conc. H₂SO₄ was refluxed for 3 h at 343 K. After cooling, the mixture was concentrated to one third of its volume under reduced pressure. The concentrated reaction mixture was kept at room temperature and light yellow crystals were obtained after five days. The crystalline product was collected, washed with methanol and dried to afford the title compound in 79% yield. Slow evaporation of a methanol solution afforded light yellow crystals suitable for single-crystal X-ray diffraction studies. All chemicals were purchased from Sigma-Aldrich.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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: SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of the O—H···N and C—H···O hydrogen bonds (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding were omitted for clarity.

2-[(2-Methoxybenzylidene)amino]phenol top

Crystal data top

C₁₄H₁₃NO₂	F(000) = 480
M_r = 227.25	D_x = 1.279 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1522 reflections
a = 9.8709 (5) Å	θ = 2.7–24.5°
b = 6.6606 (3) Å	µ = 0.09 mm⁻¹
c = 18.6128 (9) Å	T = 273 K
β = 105.249 (1)°	Block, colorless
V = 1180.63 (10) Å³	0.49 × 0.17 × 0.16 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2186 independent reflections
Radiation source: fine-focus sealed tube	1680 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scan	θ_max = 25.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.959, T_max = 0.986	k = −8→8
6660 measured reflections	l = −22→22

Refinement top

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.048P)² + 0.0868P] where P = (F_o² + 2F_c²)/3
2186 reflections	(Δ/σ)_max < 0.001
159 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₄H₁₃NO₂	V = 1180.63 (10) Å³
M_r = 227.25	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.8709 (5) Å	µ = 0.09 mm⁻¹
b = 6.6606 (3) Å	T = 273 K
c = 18.6128 (9) Å	0.49 × 0.17 × 0.16 mm
β = 105.249 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2186 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1680 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.986	R_int = 0.025
6660 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.16 e Å⁻³
2186 reflections	Δρ_min = −0.14 e Å⁻³
159 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
O1	0.93139 (12)	0.87882 (18)	0.09546 (8)	0.0651 (4)
O2	0.51633 (11)	0.57038 (17)	0.23910 (6)	0.0461 (3)
H2A	0.479 (2)	0.490 (3)	0.2663 (11)	0.073 (6)*
N1	0.57240 (12)	0.86217 (17)	0.15101 (6)	0.0371 (3)
C1	0.90429 (16)	1.0512 (2)	0.12897 (9)	0.0452 (4)
C2	0.99740 (17)	1.2103 (3)	0.14871 (9)	0.0564 (5)
H2B	1.0849	1.2044	0.1389	0.068*
C3	0.9600 (2)	1.3766 (3)	0.18280 (10)	0.0590 (5)
H3A	1.0232	1.4824	0.1962	0.071*
C4	0.83070 (19)	1.3892 (3)	0.19753 (9)	0.0546 (4)
H4A	0.8062	1.5028	0.2203	0.066*
C5	0.73841 (17)	1.2319 (2)	0.17814 (8)	0.0446 (4)
H5A	0.6511	1.2399	0.1882	0.054*
C6	0.77264 (15)	1.0608 (2)	0.14376 (8)	0.0384 (4)
C7	0.67269 (15)	0.8955 (2)	0.12140 (8)	0.0381 (4)
H7A	0.6830	0.8104	0.0836	0.046*
C8	0.47548 (14)	0.7082 (2)	0.11917 (8)	0.0351 (3)
C9	0.44428 (14)	0.5617 (2)	0.16613 (7)	0.0354 (3)
C10	0.34863 (16)	0.4124 (2)	0.13671 (9)	0.0443 (4)
H10A	0.3288	0.3132	0.1676	0.053*
C11	0.28226 (16)	0.4101 (2)	0.06126 (9)	0.0482 (4)
H11A	0.2182	0.3090	0.0418	0.058*
C12	0.31018 (17)	0.5557 (2)	0.01490 (8)	0.0484 (4)
H12A	0.2643	0.5546	−0.0356	0.058*
C13	0.40674 (16)	0.7036 (2)	0.04392 (8)	0.0441 (4)
H13A	0.4261	0.8018	0.0125	0.053*
C14	1.0695 (2)	0.8464 (3)	0.08734 (13)	0.0799 (6)
H14A	1.0744	0.7162	0.0661	0.120*
H14B	1.1361	0.8538	0.1353	0.120*
H14C	1.0910	0.9474	0.0552	0.120*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0531 (7)	0.0655 (8)	0.0875 (9)	0.0003 (6)	0.0376 (7)	−0.0084 (7)
O2	0.0529 (7)	0.0528 (7)	0.0330 (6)	−0.0114 (5)	0.0120 (5)	0.0027 (5)
N1	0.0413 (7)	0.0361 (7)	0.0367 (7)	−0.0026 (5)	0.0154 (6)	0.0003 (5)
C1	0.0434 (9)	0.0507 (10)	0.0437 (9)	−0.0014 (8)	0.0152 (7)	0.0060 (7)
C2	0.0411 (9)	0.0726 (12)	0.0549 (10)	−0.0129 (9)	0.0116 (8)	0.0120 (9)
C3	0.0628 (12)	0.0566 (11)	0.0502 (10)	−0.0233 (9)	0.0018 (9)	0.0037 (8)
C4	0.0654 (12)	0.0471 (10)	0.0487 (10)	−0.0101 (9)	0.0104 (9)	−0.0033 (8)
C5	0.0466 (9)	0.0450 (9)	0.0427 (9)	−0.0023 (8)	0.0126 (7)	0.0014 (7)
C6	0.0400 (8)	0.0394 (8)	0.0360 (8)	−0.0035 (7)	0.0100 (6)	0.0045 (6)
C7	0.0438 (9)	0.0369 (8)	0.0364 (8)	0.0000 (7)	0.0153 (7)	−0.0015 (6)
C8	0.0365 (8)	0.0357 (8)	0.0366 (8)	−0.0002 (6)	0.0159 (6)	−0.0022 (6)
C9	0.0345 (8)	0.0402 (8)	0.0337 (8)	0.0009 (6)	0.0129 (6)	0.0000 (6)
C10	0.0432 (9)	0.0440 (9)	0.0473 (9)	−0.0070 (7)	0.0145 (7)	0.0054 (7)
C11	0.0424 (9)	0.0505 (9)	0.0496 (9)	−0.0110 (7)	0.0084 (7)	−0.0063 (8)
C12	0.0485 (9)	0.0600 (10)	0.0346 (8)	−0.0048 (8)	0.0069 (7)	−0.0029 (7)
C13	0.0488 (9)	0.0484 (9)	0.0371 (8)	−0.0032 (8)	0.0149 (7)	0.0059 (7)
C14	0.0624 (12)	0.0986 (16)	0.0913 (15)	0.0195 (12)	0.0422 (11)	0.0109 (12)

Geometric parameters (Å, º) top

O1—C1	1.3665 (19)	C6—C7	1.464 (2)
O1—C14	1.427 (2)	C7—H7A	0.9300
O2—C9	1.3586 (16)	C8—C13	1.387 (2)
O2—H2A	0.88 (2)	C8—C9	1.3972 (19)
N1—C7	1.2729 (18)	C9—C10	1.382 (2)
N1—C8	1.4211 (18)	C10—C11	1.385 (2)
C1—C2	1.387 (2)	C10—H10A	0.9300
C1—C6	1.399 (2)	C11—C12	1.373 (2)
C2—C3	1.374 (3)	C11—H11A	0.9300
C2—H2B	0.9300	C12—C13	1.378 (2)
C3—C4	1.377 (3)	C12—H12A	0.9300
C3—H3A	0.9300	C13—H13A	0.9300
C4—C5	1.373 (2)	C14—H14A	0.9600
C4—H4A	0.9300	C14—H14B	0.9600
C5—C6	1.391 (2)	C14—H14C	0.9600
C5—H5A	0.9300

C1—O1—C14	118.86 (15)	C13—C8—C9	119.10 (13)
C9—O2—H2A	111.2 (13)	C13—C8—N1	122.29 (12)
C7—N1—C8	117.39 (12)	C9—C8—N1	118.55 (12)
O1—C1—C2	124.55 (15)	O2—C9—C10	123.38 (13)
O1—C1—C6	115.58 (13)	O2—C9—C8	116.88 (12)
C2—C1—C6	119.88 (15)	C10—C9—C8	119.67 (13)
C3—C2—C1	119.88 (16)	C9—C10—C11	120.10 (14)
C3—C2—H2B	120.1	C9—C10—H10A	120.0
C1—C2—H2B	120.1	C11—C10—H10A	120.0
C2—C3—C4	121.09 (16)	C12—C11—C10	120.64 (14)
C2—C3—H3A	119.5	C12—C11—H11A	119.7
C4—C3—H3A	119.5	C10—C11—H11A	119.7
C5—C4—C3	119.15 (16)	C11—C12—C13	119.40 (14)
C5—C4—H4A	120.4	C11—C12—H12A	120.3
C3—C4—H4A	120.4	C13—C12—H12A	120.3
C4—C5—C6	121.41 (15)	C12—C13—C8	121.07 (14)
C4—C5—H5A	119.3	C12—C13—H13A	119.5
C6—C5—H5A	119.3	C8—C13—H13A	119.5
C5—C6—C1	118.58 (14)	O1—C14—H14A	109.5
C5—C6—C7	121.32 (13)	O1—C14—H14B	109.5
C1—C6—C7	120.08 (13)	H14A—C14—H14B	109.5
N1—C7—C6	123.41 (13)	O1—C14—H14C	109.5
N1—C7—H7A	118.3	H14A—C14—H14C	109.5
C6—C7—H7A	118.3	H14B—C14—H14C	109.5

C14—O1—C1—C2	7.6 (2)	C1—C6—C7—N1	158.03 (14)
C14—O1—C1—C6	−171.95 (16)	C7—N1—C8—C13	−53.20 (19)
O1—C1—C2—C3	−179.47 (14)	C7—N1—C8—C9	129.61 (14)
C6—C1—C2—C3	0.1 (2)	C13—C8—C9—O2	178.76 (13)
C1—C2—C3—C4	−0.4 (3)	N1—C8—C9—O2	−3.95 (19)
C2—C3—C4—C5	0.4 (2)	C13—C8—C9—C10	1.6 (2)
C3—C4—C5—C6	−0.2 (2)	N1—C8—C9—C10	178.92 (13)
C4—C5—C6—C1	−0.1 (2)	O2—C9—C10—C11	−178.05 (14)
C4—C5—C6—C7	−178.40 (14)	C8—C9—C10—C11	−1.1 (2)
O1—C1—C6—C5	179.72 (13)	C9—C10—C11—C12	−0.2 (2)
C2—C1—C6—C5	0.1 (2)	C10—C11—C12—C13	0.9 (2)
O1—C1—C6—C7	−1.9 (2)	C11—C12—C13—C8	−0.4 (2)
C2—C1—C6—C7	178.50 (14)	C9—C8—C13—C12	−0.9 (2)
C8—N1—C7—C6	174.21 (12)	N1—C8—C13—C12	−178.09 (14)
C5—C6—C7—N1	−23.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N1ⁱ	0.88 (2)	1.94 (2)	2.796 (2)	163 (2)
C10—H10A···O2ⁱ	0.93	2.56	3.269 (2)	133

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃NO₂
M_r	227.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	9.8709 (5), 6.6606 (3), 18.6128 (9)
β (°)	105.249 (1)
V (Å³)	1180.63 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.49 × 0.17 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.959, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	6660, 2186, 1680
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.100, 1.04
No. of reflections	2186
No. of parameters	159
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.14

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N1ⁱ	0.88 (2)	1.94 (2)	2.796 (2)	163 (2)
C10—H10A···O2ⁱ	0.93	2.56	3.269 (2)	133

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

Footnotes

‡Additional corresponding author, e-mail: maslamchemist@hotmail.com.

Acknowledgements

MA express his gratitude to the Pakistan Council of Scientific and Industrial Research Laboratories Complex, Karachi, the Department of Chemistry, University of Karachi and the H·E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, for providing financial support, research facilities and X-ray diffraction facilities, respectively.

References

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