2-[(4-Chlorobenzyl)iminomethyl]phenol

Phurat, C.; Teerawatananond, T.; Muangsin, N.

doi:10.1107/S1600536810031508

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2310

https://doi.org/10.1107/S1600536810031508

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2-[(4-Chlorobenzyl)iminomethyl]phenol

Chuttree Phurat,^a Thapong Teerawatananond ^a and Nongnuj Muangsin ^a ^*

^aResearch Centre of Bioorganic Chemistry, Department of Chemistry, Faculty of, Science, Chulalongkorn University, Bangkok, 10330, Thailand
^*Correspondence e-mail: nongnuj.j@chula.ac.th

(Received 21 July 2010; accepted 5 August 2010; online 18 August 2010)

The title Schiff base compound, C₁₄H₁₂ClNO, was prepared from 4-chlorobenzylamine and salicylaldehyde. The molecule is V-shaped: the dihedral angle between the aromatic rings is 67.51 (5)°. The rings are located on the opposite side of the C=N bond, giving an E configuration. An intramolecular N—H⋯O hydrogen bond generates a S(6) ring. In the crystal structure, only weak non-classical C—H⋯O contacts are observed.

Related literature

For background to Schiff base ligands and their biological activity, see: Adsule et al. (2006 ); Karthikeyan et al. (2006 ). For related structures, see: Tariq et al. (2010 ); Khalaji & Simpson (2009 ). For the graph-set analysis of hydrogen-bond patterns, see: Bernstein et al. (1995 ). For the synthesis, see: Kannappan et al. (2005 ).

Experimental

Crystal data

C₁₄H₁₂ClNO
M_r = 245.7
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.2876 (2) Å
b = 12.2267 (3) Å
c = 16.2664 (5) Å
V = 1250.51 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 296 K
0.45 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker,2008 ) T_min = 0.933, T_max = 0.944
10586 measured reflections
1479 independent reflections
1119 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.107
S = 1.04
1479 reflections
155 parameters
143 restraints
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1	0.82	1.86	2.587 (3)	147
C11—H11⋯O1ⁱ	0.93	2.53	3.369 (4)	150
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810031508/ds2046sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810031508/ds2046Isup2.hkl

checkCIF report

Comment top

Schiff base complexes have gained importance from physiological and pharmacological activities point of view (Adsule et al., 2006). As part of our research efforts in the area of transition metal complex-based anticancer agents, the title compound has been prepared as a ligand by Schiff base reaction between 4-chlorobenzylamine and salicylaldehyde. We report herein on the crystal structure of the title compound.

The molecule adopts a V-shape structure. The dihedral angle between the chlorobenzene ring and 2-methyliminophenol moiety is 67.51 (5)°. The 2-methyliminophenol (C1 to C8, N1 and O1) moiety is nearly planar (r.m.s. deviation = 0.002 Å). The chlorobenzene and 2-methyliminophenol groups are located on the opposite side of the C=N bond, showing an E configuration. Intramolecular N—H···O hydrogen bond generates a S(6) ring. In the crystal structure, only weak non-classical C—H···O contact is observed.

Related literature top

For background to Schiff base ligands and their biological activity, see: Adsule et al. (2006); Karthikeyan et al. (2006). For related structures, see: Tariq et al. (2010); Khalaji & Simpson (2009). For the graph-set analysis of hydrogen-bond patterns, see: Bernstein et al. (1995). For the preparation, see: Kannappan et al. (2005).

Experimental top

The title compound was prepared according to the method reported in the literature (Kannappan et al., 2005). 4-Chlorobenzylamine (2.80 ml. 2.88 g, 0.02 mol) was added to a stirred ethanol solution of salicylaldehyde (2.50 ml, 2.86 g, 0.02 mol). The reaction mixture was stirred at reflux for 1 h and then the mixture was allowed to stand at room temperature for 1 week to give yellow cystals suitable for X-ray diffraction analysis.

Structure description top

For background to Schiff base ligands and their biological activity, see: Adsule et al. (2006); Karthikeyan et al. (2006). For related structures, see: Tariq et al. (2010); Khalaji & Simpson (2009). For the graph-set analysis of hydrogen-bond patterns, see: Bernstein et al. (1995). For the preparation, see: Kannappan et al. (2005).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the title compound with displacement ellipsoids for the non-hydrogen atoms drawn at the 30% probability level. Hydrogen bond is shown as dashed line.

2-[(4-Chlorobenzyl)iminomethyl]phenol top

Crystal data top

C₁₄H₁₂ClNO	F(000) = 512
M_r = 245.7	D_x = 1.305 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5069 reflections
a = 6.2876 (2) Å	θ = 2.5–22.8°
b = 12.2267 (3) Å	µ = 0.29 mm⁻¹
c = 16.2664 (5) Å	T = 296 K
V = 1250.51 (6) Å³	Prism, yellow
Z = 4	0.45 × 0.20 × 0.20 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1479 independent reflections
Radiation source: Mo Kα	1119 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
φ and ω scans	θ_max = 26.3°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker,2008)	h = −7→7
T_min = 0.933, T_max = 0.944	k = −15→15
10586 measured reflections	l = −17→20

Refinement top

Refinement on F²	143 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0436P)² + 0.2636P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.107	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.20 e Å⁻³
1479 reflections	Δρ_min = −0.29 e Å⁻³
155 parameters

Crystal data top

C₁₄H₁₂ClNO	V = 1250.51 (6) Å³
M_r = 245.7	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.2876 (2) Å	µ = 0.29 mm⁻¹
b = 12.2267 (3) Å	T = 296 K
c = 16.2664 (5) Å	0.45 × 0.20 × 0.20 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1479 independent reflections
Absorption correction: multi-scan (SADABS; Bruker,2008)	1119 reflections with I > 2σ(I)
T_min = 0.933, T_max = 0.944	R_int = 0.028
10586 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	143 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.04	Δρ_max = 0.20 e Å⁻³
1479 reflections	Δρ_min = −0.29 e Å⁻³
155 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.7530 (5)	−0.3508 (3)	0.9530 (2)	0.0818 (9)
H1	0.8887	−0.3216	0.9586	0.098*
C2	0.7031 (8)	−0.4471 (3)	0.9927 (2)	0.1008 (12)
H2	0.8045	−0.4827	1.0246	0.121*
C3	0.5038 (8)	−0.4895 (3)	0.9849 (2)	0.0974 (10)
H3	0.4697	−0.5542	1.0119	0.117*
C4	0.3524 (6)	−0.4384 (2)	0.93779 (19)	0.0815 (8)
H4	0.2173	−0.4687	0.9329	0.098*
C5	0.6053 (4)	−0.2970 (2)	0.90492 (15)	0.0587 (6)
C6	0.4010 (4)	−0.3415 (2)	0.89741 (17)	0.0616 (7)
C7	0.6613 (5)	−0.1965 (2)	0.86325 (17)	0.0711 (7)
H7	0.7986	−0.1693	0.869	0.085*
C8	0.5987 (7)	−0.0429 (3)	0.7791 (3)	0.1127 (13)
H8A	0.5962	−0.0524	0.7199	0.135*
H8B	0.7433	−0.0256	0.7954	0.135*
C9	0.4535 (6)	0.0487 (2)	0.80299 (19)	0.0789 (9)
C10	0.2539 (7)	0.0585 (3)	0.76832 (19)	0.0857 (9)
H10	0.2115	0.0083	0.7287	0.103*
C11	0.1157 (5)	0.1408 (2)	0.79093 (19)	0.0802 (8)
H11	−0.0181	0.1461	0.7669	0.096*
C12	0.1783 (5)	0.2140 (2)	0.84889 (19)	0.0748 (8)
C13	0.3760 (5)	0.2080 (3)	0.8837 (2)	0.0845 (9)
H13	0.4181	0.259	0.9228	0.101*
C14	0.5117 (5)	0.1255 (3)	0.8600 (2)	0.0877 (9)
H14	0.6466	0.1219	0.8833	0.105*
Cl1	0.00322 (17)	0.31716 (7)	0.87960 (8)	0.1204 (4)
N1	0.5305 (4)	−0.14462 (19)	0.81941 (15)	0.0780 (7)
O1	0.2507 (3)	−0.29358 (18)	0.85185 (14)	0.0864 (6)
H1A	0.2973	−0.2364	0.8325	0.13*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0706 (17)	0.0856 (19)	0.089 (2)	0.0140 (17)	−0.0191 (17)	−0.0254 (16)
C2	0.122 (3)	0.093 (2)	0.087 (2)	0.033 (2)	−0.020 (2)	−0.001 (2)
C3	0.137 (3)	0.0691 (18)	0.086 (2)	0.012 (2)	0.014 (3)	0.0082 (16)
C4	0.086 (2)	0.0660 (16)	0.092 (2)	−0.0105 (17)	0.0111 (18)	−0.0036 (16)
C5	0.0583 (13)	0.0605 (13)	0.0573 (14)	0.0023 (12)	0.0008 (12)	−0.0156 (12)
C6	0.0605 (14)	0.0610 (14)	0.0632 (15)	−0.0004 (12)	−0.0037 (13)	−0.0079 (12)
C7	0.0608 (14)	0.0639 (15)	0.0888 (19)	−0.0073 (14)	0.0169 (16)	−0.0173 (14)
C8	0.129 (3)	0.0797 (19)	0.130 (3)	0.006 (2)	0.059 (3)	0.028 (2)
C9	0.091 (2)	0.0639 (16)	0.0820 (19)	−0.0101 (16)	0.0210 (18)	0.0202 (14)
C10	0.111 (2)	0.0767 (19)	0.0700 (18)	−0.0259 (19)	0.0009 (19)	0.0051 (16)
C11	0.0789 (18)	0.0806 (18)	0.0811 (19)	−0.0202 (17)	−0.0148 (17)	0.0214 (16)
C12	0.0780 (17)	0.0599 (14)	0.0864 (19)	−0.0126 (15)	0.0028 (16)	0.0179 (14)
C13	0.090 (2)	0.0751 (17)	0.089 (2)	−0.0144 (17)	−0.0140 (19)	−0.0004 (16)
C14	0.0728 (18)	0.088 (2)	0.102 (2)	−0.0088 (19)	−0.007 (2)	0.0208 (18)
Cl1	0.1050 (7)	0.0765 (5)	0.1799 (10)	0.0032 (6)	0.0167 (8)	0.0086 (6)
N1	0.0850 (16)	0.0658 (13)	0.0831 (15)	−0.0002 (14)	0.0188 (15)	0.0061 (12)
O1	0.0654 (11)	0.0876 (15)	0.1063 (16)	−0.0097 (12)	−0.0213 (12)	0.0083 (13)

Geometric parameters (Å, º) top

C1—C2	1.379 (5)	C8—C9	1.497 (5)
C1—C5	1.380 (4)	C8—H8A	0.97
C1—H1	0.93	C8—H8B	0.97
C2—C3	1.362 (6)	C9—C14	1.369 (4)
C2—H2	0.93	C9—C10	1.381 (5)
C3—C4	1.372 (5)	C10—C11	1.379 (5)
C3—H3	0.93	C10—H10	0.93
C4—C6	1.389 (4)	C11—C12	1.358 (4)
C4—H4	0.93	C11—H11	0.93
C5—C6	1.401 (4)	C12—C13	1.367 (4)
C5—C7	1.446 (4)	C12—Cl1	1.747 (3)
C6—O1	1.336 (3)	C13—C14	1.376 (5)
C7—N1	1.260 (3)	C13—H13	0.93
C7—H7	0.93	C14—H14	0.93
C8—N1	1.470 (4)	O1—H1A	0.82

C2—C1—C5	121.3 (3)	N1—C8—H8B	109.7
C2—C1—H1	119.3	C9—C8—H8B	109.7
C5—C1—H1	119.3	H8A—C8—H8B	108.2
C3—C2—C1	119.3 (3)	C14—C9—C10	117.4 (3)
C3—C2—H2	120.3	C14—C9—C8	121.8 (3)
C1—C2—H2	120.3	C10—C9—C8	120.9 (4)
C2—C3—C4	121.1 (3)	C11—C10—C9	121.8 (3)
C2—C3—H3	119.4	C11—C10—H10	119.1
C4—C3—H3	119.4	C9—C10—H10	119.1
C3—C4—C6	120.0 (3)	C12—C11—C10	118.9 (3)
C3—C4—H4	120	C12—C11—H11	120.5
C6—C4—H4	120	C10—C11—H11	120.5
C1—C5—C6	118.7 (3)	C11—C12—C13	121.0 (3)
C1—C5—C7	120.5 (3)	C11—C12—Cl1	119.4 (3)
C6—C5—C7	120.8 (3)	C13—C12—Cl1	119.5 (3)
O1—C6—C4	118.7 (3)	C12—C13—C14	119.1 (3)
O1—C6—C5	121.8 (2)	C12—C13—H13	120.4
C4—C6—C5	119.5 (3)	C14—C13—H13	120.4
N1—C7—C5	122.3 (3)	C9—C14—C13	121.8 (3)
N1—C7—H7	118.9	C9—C14—H14	119.1
C5—C7—H7	118.9	C13—C14—H14	119.1
N1—C8—C9	109.8 (3)	C7—N1—C8	119.2 (3)
N1—C8—H8A	109.7	C6—O1—H1A	109.5
C9—C8—H8A	109.7

C5—C1—C2—C3	−0.4 (5)	N1—C8—C9—C10	−76.8 (4)
C1—C2—C3—C4	0.3 (5)	C14—C9—C10—C11	−1.2 (4)
C2—C3—C4—C6	−0.3 (5)	C8—C9—C10—C11	178.4 (3)
C2—C1—C5—C6	0.5 (4)	C9—C10—C11—C12	0.0 (4)
C2—C1—C5—C7	−179.5 (3)	C10—C11—C12—C13	1.1 (4)
C3—C4—C6—O1	179.9 (3)	C10—C11—C12—Cl1	−178.8 (2)
C3—C4—C6—C5	0.3 (4)	C11—C12—C13—C14	−0.8 (4)
C1—C5—C6—O1	−179.9 (2)	Cl1—C12—C13—C14	179.1 (2)
C7—C5—C6—O1	0.1 (4)	C10—C9—C14—C13	1.5 (4)
C1—C5—C6—C4	−0.4 (4)	C8—C9—C14—C13	−178.1 (3)
C7—C5—C6—C4	179.6 (2)	C12—C13—C14—C9	−0.6 (5)
C1—C5—C7—N1	−179.4 (3)	C5—C7—N1—C8	179.8 (3)
C6—C5—C7—N1	0.6 (4)	C9—C8—N1—C7	−124.3 (3)
N1—C8—C9—C14	102.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.82	1.86	2.587 (3)	147
C11—H11···O1ⁱ	0.93	2.53	3.369 (4)	150

Symmetry code: (i) −x, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂ClNO
M_r	245.7
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	6.2876 (2), 12.2267 (3), 16.2664 (5)
V (Å³)	1250.51 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.45 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker,2008)
T_min, T_max	0.933, 0.944
No. of measured, independent and observed [I > 2σ(I)] reflections	10586, 1479, 1119
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.107, 1.04
No. of reflections	1479
No. of parameters	155
No. of restraints	143
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.29

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.82	1.86	2.587 (3)	147.1
C11—H11···O1ⁱ	0.93	2.53	3.369 (4)	149.7

Symmetry code: (i) −x, y+1/2, −z+3/2.

Acknowledgements

This work was supported by the Research Funds from the Faculty of Science (A1B1), the Thailand Research Fund (TRF) to NM, and the Thai Government Stimulus Package 2 (TKK2555) under the Project for Establishment of Comprehensive Center for Innovative Food, Health Products and Agrigulture and Center for Petroleum Petrochemicals and Advanced Materials.

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