4-[(3-Chloro-2-methyl­phen­yl)imino­meth­yl]phenol

Abstract

In the title compound, C₁₄H₁₂ClNO, the dihedral angle between the aromatic rings is 39.84 (7)°. In th crystal, mol­ecules are connected by O—H⋯N hydrogen bonds into chains parallel to [001]. In addition, a C—H⋯π contact occurs.

Related literature  

For the bioactivity of the title compound, see: Corke et al. (1979 ▶); Gorrad & Manson (1989 ▶). For related structures, see: Jothi et al. (2012 ▶); Yaeghoobi et al. (2009 ▶).

Experimental  

Crystal data  

• C₁₄H₁₂ClNO

• M _r = 245.70

• Orthorhombic,

• a = 7.5271 (9) Å

• b = 12.4095 (15) Å

• c = 12.5800 (14) Å

• V = 1175.1 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 0.31 mm⁻¹

• T = 103 K

• 0.26 × 0.20 × 0.18 mm

Data collection  

• Oxford Diffraction Xcalibur Eos diffractometer

• 6050 measured reflections

• 2042 independent reflections

• 1856 reflections with I > 2σ(I)

• R _int = 0.037

Refinement  

• R[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 0.123

• S = 1.07

• 2042 reflections

• 155 parameters

• H-atom parameters constrained

• Δρ_max = 0.71 e Å⁻³

• Δρ_min = −0.46 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg is the centroid of the C11–C16 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N3i	0.84	2.05	2.854 (3)	160
C17—H17C⋯Cg ii	0.98	2.73	3.649 (2)	157

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The investigation of microbial degradation by hazardous compounds such as anilines containing a methyl and a chlorosubstituent is of interest because of their lipophilic character and affinity to interact with DNA (Gorrad & Manson, 1989).

The ORTEP drawing of the title molecule is shown in Fig. 1. The 4-hydroxybenzylidene system is nearly planar and its geometry is similar to 4-chloro-2-[(E)-2-(4-methoxyphenyl)-ethyliminomethyl]phenol (Yaeghoobi et al., 2009). The dihedral angle between the methylphenol and chloromethylphenylimino ring systems is 39.84 (7)°.

The molecules are connected by O—H···N interactions into chains along the [0 0 1] direction (Fig. 2). There is a weak contact of the type C—H···π [1/2-x,-y,-1/2+z] with a C···Cg distance of 3.649 (2) Å between the methyl group of the chloromethyl ring and the phenol ring.

Experimental

Equimolar concentrations of 4-hydoxybenzaldehyde (0.003 mol) and 3-chloro-2-methylbenzenamine (0.003 mol) were refluxed for 5 h using methanol (25 ml) as solvent. The progress of the reaction was followed by TLC until the reaction was complete. The reaction product was cooled to 273 K. The precipitate was filtered and washed with diethyl ether. The residue was recrystallized from methanol. Brown single crystals were obtained.

Refinement

In the absence of significant anomalous dispersion effects Friedel pairs have been merged. All the hydrogen atoms of the compound are fixed geometrically (O—H = 0.88 Å and C—H= 0.93–0.97 Å) and allowed to ride on their parent atoms.

Figures

Fig. 1.

ORTEP diagram of the title compound with 50% probability ellipsoids.

Fig. 2.

Packing diagram of the title compound, viewed along [1 - 1 0] direction. O—H···N hydrogen bonds are indicated by dashed lines.

Crystal data

C14H12ClNO	F(000) = 512
Mr = 245.70	Dx = 1.389 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2042 reflections
a = 7.5271 (9) Å	θ = 2.3–30.6°
b = 12.4095 (15) Å	µ = 0.31 mm−1
c = 12.5800 (14) Å	T = 103 K
V = 1175.1 (2) Å3	Block, brown
Z = 4	0.26 × 0.20 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer	1856 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
Graphite monochromator	θmax = 30.6°, θmin = 2.3°
Detector resolution: 16.0839 pixels mm-1	h = −10→7
ω scans	k = −17→16
6050 measured reflections	l = −16→17
2042 independent reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0838P)2 + 0.0338P] where P = (Fo2 + 2Fc2)/3
2042 reflections	(Δ/σ)max < 0.001
155 parameters	Δρmax = 0.71 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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	0.20725 (8)	0.07415 (5)	0.21487 (5)	0.0206 (2)
O2	−0.2400 (2)	0.06296 (14)	1.08991 (14)	0.0200 (5)
N3	−0.0186 (3)	0.11403 (16)	0.60025 (16)	0.0151 (5)
C4	0.0219 (3)	0.16256 (18)	0.50001 (19)	0.0142 (6)
C5	0.0934 (3)	0.09792 (18)	0.41844 (19)	0.0144 (6)
C6	0.1173 (3)	0.1473 (2)	0.31955 (19)	0.0147 (6)
C7	0.0749 (3)	0.2551 (2)	0.3006 (2)	0.0182 (7)
C8	0.0060 (3)	0.3171 (2)	0.3831 (2)	0.0192 (7)
C9	−0.0203 (3)	0.27089 (18)	0.4822 (2)	0.0165 (6)
C10	0.0205 (3)	0.16597 (19)	0.68499 (19)	0.0157 (6)
C11	−0.0336 (3)	0.13243 (19)	0.79125 (19)	0.0146 (6)
C12	−0.1136 (3)	0.03193 (19)	0.81002 (19)	0.0162 (6)
C13	−0.1794 (3)	0.00693 (19)	0.91011 (19)	0.0154 (6)
C14	−0.1689 (3)	0.08211 (19)	0.99228 (18)	0.0148 (6)
C15	−0.0820 (3)	0.18052 (19)	0.9758 (2)	0.0170 (6)
C16	−0.0153 (3)	0.20481 (19)	0.8757 (2)	0.0161 (6)
C17	0.1424 (3)	−0.01811 (19)	0.4369 (2)	0.0191 (7)
H2	−0.28810	0.00190	1.09040	0.0300*
H7	0.09280	0.28580	0.23230	0.0220*
H8	−0.02280	0.39070	0.37150	0.0230*
H9	−0.06730	0.31310	0.53850	0.0200*
H10	0.08860	0.23010	0.67830	0.0190*
H12	−0.12270	−0.01910	0.75400	0.0190*
H13	−0.23160	−0.06160	0.92270	0.0180*
H15	−0.06890	0.23030	1.03260	0.0200*
H16	0.04360	0.27160	0.86450	0.0190*
H17A	0.09600	−0.06240	0.37870	0.0290*
H17B	0.09100	−0.04250	0.50440	0.0290*
H17C	0.27200	−0.02500	0.43980	0.0290*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0193 (3)	0.0256 (3)	0.0169 (3)	−0.0005 (2)	0.0037 (2)	−0.0025 (2)
O2	0.0225 (9)	0.0216 (8)	0.0160 (8)	−0.0038 (7)	0.0057 (7)	−0.0002 (7)
N3	0.0108 (9)	0.0184 (9)	0.0160 (9)	−0.0002 (7)	0.0016 (8)	0.0019 (7)
C4	0.0096 (10)	0.0162 (10)	0.0168 (11)	−0.0014 (8)	0.0009 (9)	0.0013 (8)
C5	0.0083 (9)	0.0180 (10)	0.0170 (11)	−0.0006 (8)	−0.0017 (9)	0.0008 (8)
C6	0.0082 (9)	0.0213 (10)	0.0146 (10)	−0.0013 (8)	0.0015 (8)	−0.0017 (8)
C7	0.0150 (11)	0.0215 (11)	0.0180 (12)	−0.0024 (9)	0.0001 (9)	0.0043 (9)
C8	0.0147 (11)	0.0183 (11)	0.0246 (12)	−0.0002 (9)	−0.0011 (10)	0.0039 (9)
C9	0.0108 (10)	0.0173 (11)	0.0214 (12)	0.0014 (8)	0.0012 (9)	−0.0009 (9)
C10	0.0108 (10)	0.0171 (10)	0.0191 (11)	0.0005 (8)	0.0020 (9)	0.0000 (8)
C11	0.0104 (9)	0.0191 (10)	0.0144 (10)	0.0004 (8)	0.0002 (9)	0.0009 (9)
C12	0.0133 (10)	0.0189 (10)	0.0164 (11)	0.0002 (8)	−0.0002 (9)	−0.0003 (8)
C13	0.0121 (10)	0.0175 (10)	0.0167 (10)	−0.0003 (8)	0.0017 (9)	0.0002 (9)
C14	0.0121 (9)	0.0175 (10)	0.0148 (10)	0.0013 (8)	0.0016 (8)	0.0001 (8)
C15	0.0172 (11)	0.0178 (10)	0.0160 (11)	−0.0013 (9)	−0.0001 (10)	−0.0026 (8)
C16	0.0135 (11)	0.0151 (10)	0.0196 (11)	−0.0014 (8)	−0.0012 (9)	0.0008 (9)
C17	0.0185 (12)	0.0180 (11)	0.0207 (12)	0.0029 (9)	0.0033 (10)	0.0003 (9)

Geometric parameters (Å, º)

Cl1—C6	1.737 (2)	C12—C13	1.388 (3)
O2—C14	1.361 (3)	C13—C14	1.395 (3)
O2—H2	0.8400	C14—C15	1.401 (3)
N3—C4	1.430 (3)	C15—C16	1.389 (4)
N3—C10	1.280 (3)	C7—H7	0.9500
C4—C9	1.399 (3)	C8—H8	0.9500
C4—C5	1.409 (3)	C9—H9	0.9500
C5—C6	1.398 (3)	C10—H10	0.9500
C5—C17	1.504 (3)	C12—H12	0.9500
C6—C7	1.396 (3)	C13—H13	0.9500
C7—C8	1.392 (3)	C15—H15	0.9500
C8—C9	1.386 (4)	C16—H16	0.9500
C10—C11	1.458 (3)	C17—H17A	0.9800
C11—C16	1.398 (3)	C17—H17B	0.9800
C11—C12	1.405 (3)	C17—H17C	0.9800
C14—O2—H2	109.00	C11—C16—C15	120.9 (2)
C4—N3—C10	118.2 (2)	C6—C7—H7	120.00
N3—C4—C5	118.9 (2)	C8—C7—H7	120.00
C5—C4—C9	121.1 (2)	C7—C8—H8	120.00
N3—C4—C9	119.8 (2)	C9—C8—H8	120.00
C4—C5—C6	116.6 (2)	C4—C9—H9	120.00
C4—C5—C17	121.7 (2)	C8—C9—H9	120.00
C6—C5—C17	121.7 (2)	N3—C10—H10	118.00
Cl1—C6—C5	119.71 (18)	C11—C10—H10	118.00
Cl1—C6—C7	117.42 (18)	C11—C12—H12	120.00
C5—C6—C7	122.9 (2)	C13—C12—H12	120.00
C6—C7—C8	119.2 (2)	C12—C13—H13	120.00
C7—C8—C9	119.7 (2)	C14—C13—H13	120.00
C4—C9—C8	120.6 (2)	C14—C15—H15	120.00
N3—C10—C11	123.8 (2)	C16—C15—H15	120.00
C10—C11—C16	119.1 (2)	C11—C16—H16	120.00
C12—C11—C16	119.0 (2)	C15—C16—H16	119.00
C10—C11—C12	121.8 (2)	C5—C17—H17A	110.00
C11—C12—C13	120.3 (2)	C5—C17—H17B	109.00
C12—C13—C14	120.2 (2)	C5—C17—H17C	109.00
O2—C14—C13	122.0 (2)	H17A—C17—H17B	109.00
O2—C14—C15	118.0 (2)	H17A—C17—H17C	109.00
C13—C14—C15	120.0 (2)	H17B—C17—H17C	109.00
C14—C15—C16	119.5 (2)
C10—N3—C4—C5	138.4 (2)	C6—C7—C8—C9	−0.4 (3)
C10—N3—C4—C9	−45.7 (3)	C7—C8—C9—C4	0.0 (3)
C4—N3—C10—C11	171.9 (2)	N3—C10—C11—C12	8.7 (4)
N3—C4—C5—C6	175.1 (2)	N3—C10—C11—C16	−167.4 (2)
N3—C4—C5—C17	−5.2 (3)	C10—C11—C12—C13	−173.6 (2)
C9—C4—C5—C6	−0.8 (3)	C16—C11—C12—C13	2.5 (3)
C9—C4—C5—C17	178.9 (2)	C10—C11—C16—C15	173.2 (2)
N3—C4—C9—C8	−175.3 (2)	C12—C11—C16—C15	−2.9 (3)
C5—C4—C9—C8	0.6 (3)	C11—C12—C13—C14	1.0 (3)
C4—C5—C6—Cl1	179.21 (17)	C12—C13—C14—O2	176.5 (2)
C4—C5—C6—C7	0.5 (3)	C12—C13—C14—C15	−4.0 (3)
C17—C5—C6—Cl1	−0.5 (3)	O2—C14—C15—C16	−177.0 (2)
C17—C5—C6—C7	−179.2 (2)	C13—C14—C15—C16	3.5 (3)
Cl1—C6—C7—C8	−178.66 (18)	C14—C15—C16—C11	0.0 (3)
C5—C6—C7—C8	0.1 (3)

Hydrogen-bond geometry (Å, º)

Cg is the centroid of the C11–C16 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N3i	0.84	2.05	2.854 (3)	160
C12—H12···O2ii	0.95	2.37	3.204 (3)	146
C17—H17B···N3	0.98	2.43	2.895 (3)	108
C17—H17C···Cgiii	0.98	2.73	3.649 (2)	157

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