2-[(E)-(2-Chloro­phen­yl)imino­meth­yl]-6-methyl­phenol

Abstract

The title compound, C₁₄H₁₂ClNO, a Schiff base derived from 3-methyl­salicyl­aldehyde, crystallizes in the phenol–imine tautomeric form with an E conformation for the imine functionality. The mol­ecule is not planar, the dihedral angle between the aromatic rings being 36.38 (5)°. The hy­droxy H atom is involved in a strong intra­molecular O—H⋯N hydrogen bond, generating an S(6) ring.

Related literature

For background information and applications of Schiff base complexes, see: Barton & Ollis (1979 ▶); Layer (1963 ▶); Ingold (1969 ▶); Cohen et al. (1964 ▶); Henrici-Olive & Olive (1984 ▶); Garnovskii et al. (1993 ▶). For related structures, see: Köysal et al. (2007 ▶); Kılıç et al. (2009 ▶); Şahin et al. (2009 ▶).

Experimental

Crystal data

• C₁₄H₁₂ClNO

• M _r = 245.70

• Orthorhombic,

• a = 7.8318 (14) Å

• b = 11.693 (2) Å

• c = 13.250 (2) Å

• V = 1213.4 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.30 mm⁻¹

• T = 293 K

• 0.21 × 0.11 × 0.06 mm

Data collection

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.940, T _max = 0.982

• 6803 measured reflections

• 2477 independent reflections

• 1486 reflections with I > 2σ(I)

• R _int = 0.070

Refinement

• R[F ² > 2σ(F ²)] = 0.051

• wR(F ²) = 0.096

• S = 1.00

• 2477 reflections

• 158 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.15 e Å⁻³

• Δρ_min = −0.14 e Å⁻³

• Absolute structure: Flack (1983 ▶), 1034 Friedel pairs

• Flack parameter: −0.06 (9)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; 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.

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
O1—H1⋯N1	0.87 (1)	1.84 (2)	2.615 (3)	148 (3)

supplementary crystallographic information

Comment

Schiff bases are used as starting materials in the synthesis of important drugs (Layer, 1963; Ingold, 1969). A large number of Schiff bases and their complexes have been studied for their interesting and important properties, e.g. catalytic activity (Henrici-Olive & Olive, 1984), photochromic properties (Cohen et al., 1964), biological activity (Barton et al., 1979). On the other hand, Schiff base ligands play a vital role in coordination chemistry due to their metal binding ability (Garnovskii et al., 1993).

The structure of the title compound is shown in Fig. 1. The C7═N1 double bond of 1.283 (3) Å is slightly longer than the literature values found in similar structures (Köysal et al., 2007; Kılıç et al., 2009; Şahin et al., 2009) in the range of 1.262 (8)-1.279 (3) Å. The title molecule is not planar with a dihedral angle between the aromatic rings C1/C6 and C8/C13 of 36.38 (5) °. The imino group is coplanar with the hydroxyphenyl ring with the torsion angle C13—C8—C7—N1 of 1.6 (4) °.

The molecular structure is stabilized by a strong intramolecular O—H···N hydrogen bond.

Experimental

A solution of 3-methylsalicylaldehyde (0.0681 g, 0.5 mmol) in ethanol (10 ml) was added to a solution of 2-chlorobenzenamine (0.0638 g, 0.5 mmol) in ethanol (20 ml). The reaction mixture was stirred for 2 h under reflux. Single crystals suitable for a X-ray analysis were obtained from ethanol by slow evaporation (0.0749 g, 61%).

Refinement

The H atom bounded to O1 was located in the difference Fourier map and freely refined with U_iso(H) = 1.2U_eq (O). All other H atoms were placed in calculated positions and refined using a riding-model approximation with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, and with C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms.

Figures

Fig. 1.

The molecular structure of the title compound, with the atom-numbering scheme and 25% probability displacement ellipsoids for the non-H atoms.

Crystal data

C14H12ClNO	F(000) = 512
Mr = 245.70	Dx = 1.345 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1163 reflections
a = 7.8318 (14) Å	θ = 3.1–28.8°
b = 11.693 (2) Å	µ = 0.30 mm−1
c = 13.250 (2) Å	T = 293 K
V = 1213.4 (4) Å3	Needle, yellow
Z = 4	0.21 × 0.11 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	2477 independent reflections
Radiation source: fine-focus sealed tube	1486 reflections with I > 2σ(I)
graphite	Rint = 0.070
φ and ω scans	θmax = 26.4°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −9→9
Tmin = 0.940, Tmax = 0.982	k = −14→14
6803 measured reflections	l = −16→16

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096	w = 1/[σ2(Fo2) + (0.0358P)2 + 0.0414P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
2477 reflections	Δρmax = 0.15 e Å−3
158 parameters	Δρmin = −0.14 e Å−3
1 restraint	Absolute structure: Flack (1983), 1034 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.06 (9)

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	−0.30427 (11)	−0.84282 (9)	−0.18201 (8)	0.0873 (3)
C11	−0.2023 (4)	−0.5269 (3)	−0.6436 (3)	0.0609 (9)
H11	−0.1358	−0.4949	−0.6945	0.073*
C2	−0.6147 (5)	−0.8244 (3)	−0.0959 (3)	0.0673 (9)
H2	−0.5727	−0.8740	−0.0469	0.081*
C4	−0.8405 (4)	−0.7124 (3)	−0.1622 (3)	0.0704 (10)
H4	−0.9518	−0.6851	−0.1577	0.085*
C13	−0.2304 (4)	−0.5959 (2)	−0.4763 (2)	0.0460 (7)
N1	−0.4592 (3)	−0.68266 (18)	−0.32559 (19)	0.0510 (6)
C8	−0.4038 (3)	−0.6210 (2)	−0.4942 (2)	0.0446 (7)
C5	−0.7384 (3)	−0.6793 (3)	−0.2418 (3)	0.0600 (8)
H5	−0.7817	−0.6305	−0.2910	0.072*
C1	−0.5125 (4)	−0.7905 (2)	−0.1741 (2)	0.0546 (8)
C3	−0.7793 (5)	−0.7849 (3)	−0.0899 (3)	0.0726 (10)
H3	−0.8492	−0.8075	−0.0368	0.087*
C9	−0.4702 (4)	−0.5986 (2)	−0.5894 (2)	0.0568 (8)
H9	−0.5835	−0.6167	−0.6030	0.068*
C7	−0.5128 (3)	−0.6658 (2)	−0.4159 (2)	0.0476 (7)
H7	−0.6257	−0.6830	−0.4313	0.057*
C12	−0.1285 (3)	−0.5488 (2)	−0.5514 (2)	0.0509 (8)
C6	−0.5706 (3)	−0.7186 (2)	−0.2491 (2)	0.0495 (7)
C10	−0.3721 (4)	−0.5507 (3)	−0.6631 (2)	0.0638 (9)
H10	−0.4190	−0.5342	−0.7260	0.077*
C14	0.0568 (4)	−0.5250 (3)	−0.5305 (3)	0.0781 (11)
H14C	0.1143	−0.5953	−0.5150	0.117*
H14A	0.0662	−0.4737	−0.4742	0.117*
H14B	0.1081	−0.4907	−0.5889	0.117*
O1	−0.1569 (2)	−0.61668 (18)	−0.38591 (17)	0.0618 (6)
H1	−0.233 (3)	−0.648 (3)	−0.3472 (19)	0.074*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0762 (5)	0.1058 (7)	0.0799 (7)	0.0203 (5)	−0.0073 (5)	0.0146 (6)
C11	0.072 (2)	0.0524 (19)	0.058 (2)	0.0033 (17)	0.0238 (19)	0.0008 (17)
C2	0.089 (3)	0.054 (2)	0.059 (2)	−0.0124 (19)	−0.002 (2)	0.0131 (19)
C4	0.064 (2)	0.065 (2)	0.083 (3)	−0.0066 (17)	0.016 (2)	0.000 (2)
C13	0.0515 (19)	0.0393 (16)	0.0471 (19)	0.0069 (13)	0.0008 (15)	−0.0042 (15)
N1	0.0543 (13)	0.0510 (14)	0.0477 (16)	−0.0051 (11)	0.0029 (14)	0.0016 (14)
C8	0.0473 (18)	0.0412 (17)	0.0452 (19)	0.0026 (12)	0.0044 (15)	−0.0075 (15)
C5	0.0581 (18)	0.0538 (19)	0.068 (2)	−0.0021 (15)	0.0058 (17)	0.0120 (18)
C1	0.0629 (18)	0.0511 (16)	0.0499 (19)	−0.0042 (15)	−0.0015 (18)	−0.0013 (18)
C3	0.087 (3)	0.064 (2)	0.067 (2)	−0.0186 (19)	0.022 (2)	0.002 (2)
C9	0.0564 (17)	0.0652 (18)	0.049 (2)	0.0009 (15)	−0.0027 (17)	−0.0051 (19)
C7	0.0468 (15)	0.0460 (16)	0.050 (2)	−0.0023 (14)	−0.0025 (16)	−0.0025 (17)
C12	0.0527 (17)	0.0432 (16)	0.057 (2)	0.0023 (14)	0.0098 (18)	−0.0034 (16)
C6	0.0539 (18)	0.0423 (16)	0.0523 (19)	−0.0094 (13)	0.0014 (16)	−0.0013 (17)
C10	0.079 (2)	0.071 (2)	0.042 (2)	0.0057 (18)	0.0028 (18)	−0.0004 (19)
C14	0.057 (2)	0.085 (2)	0.093 (3)	−0.0041 (17)	0.0114 (19)	0.004 (2)
O1	0.0516 (12)	0.0784 (16)	0.0554 (15)	−0.0011 (11)	−0.0025 (11)	0.0044 (12)

Geometric parameters (Å, °)

Cl1—C1	1.745 (3)	C8—C9	1.388 (4)
C11—C12	1.376 (4)	C8—C7	1.442 (4)
C11—C10	1.384 (4)	C5—C6	1.396 (4)
C11—H11	0.9300	C5—H5	0.9300
C2—C1	1.369 (4)	C1—C6	1.378 (4)
C2—C3	1.372 (4)	C3—H3	0.9300
C2—H2	0.9300	C9—C10	1.363 (4)
C4—C3	1.366 (4)	C9—H9	0.9300
C4—C5	1.379 (4)	C7—H7	0.9300
C4—H4	0.9300	C12—C14	1.503 (4)
C13—O1	1.351 (3)	C10—H10	0.9300
C13—C12	1.389 (4)	C14—H14C	0.9600
C13—C8	1.410 (4)	C14—H14A	0.9600
N1—C7	1.283 (3)	C14—H14B	0.9600
N1—C6	1.402 (3)	O1—H1	0.87 (3)
C12—C11—C10	122.2 (3)	C2—C3—H3	120.1
C12—C11—H11	118.9	C10—C9—C8	121.2 (3)
C10—C11—H11	118.9	C10—C9—H9	119.4
C1—C2—C3	119.7 (3)	C8—C9—H9	119.4
C1—C2—H2	120.1	N1—C7—C8	122.2 (3)
C3—C2—H2	120.1	N1—C7—H7	118.9
C3—C4—C5	120.5 (3)	C8—C7—H7	118.9
C3—C4—H4	119.8	C11—C12—C13	117.9 (3)
C5—C4—H4	119.8	C11—C12—C14	122.3 (3)
O1—C13—C12	117.5 (3)	C13—C12—C14	119.8 (3)
O1—C13—C8	121.4 (3)	C1—C6—C5	117.5 (3)
C12—C13—C8	121.1 (3)	C1—C6—N1	119.9 (3)
C7—N1—C6	121.1 (2)	C5—C6—N1	122.5 (3)
C9—C8—C13	118.3 (3)	C9—C10—C11	119.3 (3)
C9—C8—C7	120.0 (3)	C9—C10—H10	120.3
C13—C8—C7	121.7 (3)	C11—C10—H10	120.3
C4—C5—C6	120.4 (3)	C12—C14—H14C	109.5
C4—C5—H5	119.8	C12—C14—H14A	109.5
C6—C5—H5	119.8	H14C—C14—H14A	109.5
C2—C1—C6	122.0 (3)	C12—C14—H14B	109.5
C2—C1—Cl1	119.4 (3)	H14C—C14—H14B	109.5
C6—C1—Cl1	118.6 (2)	H14A—C14—H14B	109.5
C4—C3—C2	119.9 (3)	C13—O1—H1	108 (2)
C4—C3—H3	120.1
O1—C13—C8—C9	−179.2 (2)	C10—C11—C12—C14	178.9 (3)
C12—C13—C8—C9	0.7 (4)	O1—C13—C12—C11	−179.7 (2)
O1—C13—C8—C7	2.5 (4)	C8—C13—C12—C11	0.4 (4)
C12—C13—C8—C7	−177.6 (2)	O1—C13—C12—C14	1.0 (4)
C3—C4—C5—C6	−0.6 (4)	C8—C13—C12—C14	−178.9 (3)
C3—C2—C1—C6	−1.1 (5)	C2—C1—C6—C5	1.1 (4)
C3—C2—C1—Cl1	−179.1 (3)	Cl1—C1—C6—C5	179.1 (2)
C5—C4—C3—C2	0.6 (5)	C2—C1—C6—N1	177.5 (3)
C1—C2—C3—C4	0.2 (5)	Cl1—C1—C6—N1	−4.5 (3)
C13—C8—C9—C10	−1.8 (4)	C4—C5—C6—C1	−0.2 (4)
C7—C8—C9—C10	176.5 (3)	C4—C5—C6—N1	−176.6 (3)
C6—N1—C7—C8	175.4 (2)	C7—N1—C6—C1	146.1 (3)
C9—C8—C7—N1	−176.7 (3)	C7—N1—C6—C5	−37.6 (4)
C13—C8—C7—N1	1.6 (4)	C8—C9—C10—C11	1.8 (5)
C10—C11—C12—C13	−0.4 (4)	C12—C11—C10—C9	−0.7 (5)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.87 (1)	1.84 (2)	2.615 (3)	148 (3)