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

Manjunath, B.C.; Abdoh, M.M.M.; Mallesha, L.; Mohana, K.N.; Lokanath, N.K.

doi:10.1107/S1600536812043140

organic compounds

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Volume 68| Part 11| November 2012| Page o3191

doi:10.1107/S1600536812043140

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

B. C. Manjunath,^a M. M. M Abdoh,^b L. Mallesha,^c K. N. Mohana ^d and N. K. Lokanath ^a ^*

^aDepartment of Studies in Physics, Manasagangotri, University of Mysore, Mysore 570 006, India, ^bDepartment of Physics, Faculty of Science, An Najah National University, Nabtus West Bank, Palestinian Territories, ^cPG Department of Studies in Chemistry, JSS College of Arts Commerce and Science, Ooty Road, Mysore 570 025, India, and ^dDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India
^*Correspondence e-mail: lokanath@physics.uni-mysore.ac.in

(Received 5 September 2012; accepted 16 October 2012; online 20 October 2012)

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, P 2₁ 2₁ 2₁
a = 7.5271 (9) Å
b = 12.4095 (15) Å
c = 12.5800 (14) Å
V = 1175.1 (2) Å³
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[F² > 2σ(F²)] = 0.047
wR(F²) = 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

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⋯Cgⁱⁱ	0.98	2.73	3.649 (2)	157
Symmetry codes: (i) $[-x-{\script{1\over 2}}, -y, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812043140/kj2211sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043140/kj2211Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812043140/kj2211Isup3.cml

checkCIF report

Comment top

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.

Related literature top

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 top

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.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); 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).

Figures top

	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.

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

Crystal data top

C₁₄H₁₂ClNO	F(000) = 512
M_r = 245.70	D_x = 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 top

Oxford Diffraction Xcalibur Eos diffractometer	1856 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.037
Graphite monochromator	θ_max = 30.6°, θ_min = 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 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0838P)² + 0.0338P] where P = (F_o² + 2F_c²)/3
2042 reflections	(Δ/σ)_max < 0.001
155 parameters	Δρ_max = 0.71 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₁₄H₁₂ClNO	V = 1175.1 (2) Å³
M_r = 245.70	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.5271 (9) Å	µ = 0.31 mm⁻¹
b = 12.4095 (15) Å	T = 103 K
c = 12.5800 (14) Å	0.26 × 0.20 × 0.18 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	1856 reflections with I > 2σ(I)
6050 measured reflections	R_int = 0.037
2042 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.07	Δρ_max = 0.71 e Å⁻³
2042 reflections	Δρ_min = −0.46 e Å⁻³
155 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂ClNO
M_r	245.70
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	103
a, b, c (Å)	7.5271 (9), 12.4095 (15), 12.5800 (14)
V (Å³)	1175.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.26 × 0.20 × 0.18

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6050, 2042, 1856
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.123, 1.07
No. of reflections	2042
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.46

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C11–C16 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N3ⁱ	0.8400	2.0500	2.854 (3)	160.00
C17—H17C···Cgⁱⁱ	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.

References

Corke, T. C., Bunce, N. J., Beamount, A. L. & Merrick, R. L. (1979). J. Agric. Food Chem. 27, 644–646. CrossRef CAS Web of Science Google Scholar
Gorrad, J. W. & Manson, D. (1989). Xenobiotica, 16, 933–955. Google Scholar
Jothi, L., Vasuki, G., Babu, R. R. & Ramamurthi, K. (2012). Acta Cryst. E68, o772. CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yaeghoobi, M., Rahman, N. A. & Ng, S. W. (2009). Acta Cryst. E65, o1070. Web of Science CSD CrossRef IUCr Journals Google Scholar

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doi:10.1107/S1600536812043140

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