2-[(E)-(5-Chloro-2-methyl­phen­yl)imino­meth­yl]-4-methyl­phenol

Zheng, Y.-F.

doi:10.1107/S1600536813019454

organic compounds

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Volume 69| Part 8| August 2013| Page o1349

doi:10.1107/S1600536813019454

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2-[(E)-(5-Chloro-2-methylphenyl)iminomethyl]-4-methylphenol

Yun-Fa Zheng ^a ^*

^aDepartment of Chemistry, Lishui University, Lishui 323000, People's Republic of China
^*Correspondence e-mail: fan200203@163.com

(Received 10 July 2013; accepted 14 July 2013; online 27 July 2013)

In the molecule of the title Schiff base compound, C₁₅H₁₄ClNO, the two benzene rings are twisted with respect to each other, with a dihedral angle of 35.0 (3)°; an intramolecular O—H⋯N hydrogen bond occurs. In the crystal, weak C—H⋯π interactions between methyl groups and chlorophenyl rings link the molecules into supramolecular chains running along the a axis.

Related literature

For background to phyenylamine compounds, see: Fan et al. (2012 ). For applications of Schiff base derivatives, see: Siddiqui et al. (2006 ); Ebrahimipour et al. (2012 ).

Experimental

Crystal data

C₁₅H₁₄ClNO
M_r = 259.72
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.6629 (10) Å
b = 11.8442 (14) Å
c = 14.342 (2) Å
V = 1301.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 293 K
0.45 × 0.42 × 0.35 mm

Data collection

Agilent Xcalibur Gemini ultra diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.88, T_max = 0.91
8663 measured reflections
2382 independent reflections
1769 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.100
S = 1.03
2382 reflections
169 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), with 991 Friedel pairs
Absolute structure parameter: −0.18 (9)

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C9–C14 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.84 (4)	1.84 (4)	2.629 (3)	154 (4)
C7—H7C⋯Cg1ⁱ	0.96	2.91	3.767 (3)	149
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z+1]$ .

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813019454/xu5720sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813019454/xu5720Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813019454/xu5720Isup3.cml

checkCIF report

Comment top

Phyenylamine group has received attention in recent years for their unique physical and chemical properties (Fan et al., 2012). On the other hand, Schiff bases derived from salicyladehyde and methylaniline with varous substituents have exhibited potential application in pharmaceutical field for their properties of antitumor, antimicrobial and antiviral activities (Siddiqui et al., 2006). Moreover, Schiff bases ligands are potentially capable of forming stable complexes by coordination of metal ions with their nitrogen donors (Ebrahimipour et al., 2012). As an extension work on the structural characterization of Schiff base compounds, the title compound is reported.

The molecular structure of title compound shows an E configuration, with a C9—N1═C8—C6 torsion angle of 0.26 (4)°. The bond distance of N1═C8 at 1.284 (3)Å is a typical double bond. It is noteworthy that H1 atom bonded to O1 is involved in an O1—H1···N1 intramolecular hydrogen bond, which results in formation of a six-membered ring (Fig. 1). The dihedral angle between the two planes of the chlorophyenyl ring and methylphenol ring is 35.0 (3)°.

Related literature top

For background to phyenylamine compounds, see: Fan et al. (2012). For applications of Schiff base derivatives, see: Siddiqui et al. (2006); Ebrahimipour et al. (2012).

Experimental top

A mixture of 5-chloro-2-methylaniline (1.42g, 10.0 mmol), 3-methyl-2-hydroxybenzaldehyde (1.36g, 10.0 mmol) in 50.0 ml CH₂Cl₂ was fluxed under an Ar atmosphere for about 6 h to gain a yellow precipitate. The product was collected by filtration and washed with cold ethanol to give the Schiff base compound (2.25g in 86% yield). The yellow single crystals suitable for X-ray analysis were crystallized from CH₂Cl₂/absolute ethanol (3/2) systems by slow evaporation of solvents at room temperature over a week. Elemental analysis. Calc. for C₁₅H₁₄ClNO: C 69.36, H, 6.43%; Found C 69.92, H 6.80%.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Thermal ellipsoid plot of the title compound. Ellipsoids are drawn at the 50% probability level and H atoms are represented as small spheres of arbitrary radius. The dashed line indicates the intramolecular hydrogen bond.
	Fig. 2. Thermal ellipsoid plot of the title compound. Ellipsoids are drawn at the 50% probability level and H atoms are represented as small spheres of arbitrary radius.

2-[(E)-(5-Chloro-2-methylphenyl)iminomethyl]-4-methylphenol top

Crystal data top

C₁₅H₁₄ClNO	F(000) = 544
M_r = 259.72	D_x = 1.325 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1894 reflections
a = 7.6629 (10) Å	θ = 3.4–29.6°
b = 11.8442 (14) Å	µ = 0.28 mm⁻¹
c = 14.342 (2) Å	T = 293 K
V = 1301.7 (3) Å³	Block, yellow
Z = 4	0.45 × 0.42 × 0.35 mm

Data collection top

Agilent Xcalibur Gemini ultra diffractometer with Atlas detector	2382 independent reflections
Radiation source: fine-focus sealed tube	1769 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 10.3592 pixels mm^-1	θ_max = 25.4°, θ_min = 3.4°
ω scans	h = −9→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −14→14
T_min = 0.88, T_max = 0.91	l = −15→17
8663 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.041	w = 1/[σ²(F_o²) + (0.0463P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.100	(Δ/σ)_max = 0.002
S = 1.03	Δρ_max = 0.16 e Å⁻³
2382 reflections	Δρ_min = −0.17 e Å⁻³
169 parameters	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.024 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with 991 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.18 (9)

Crystal data top

C₁₅H₁₄ClNO	V = 1301.7 (3) Å³
M_r = 259.72	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.6629 (10) Å	µ = 0.28 mm⁻¹
b = 11.8442 (14) Å	T = 293 K
c = 14.342 (2) Å	0.45 × 0.42 × 0.35 mm

Data collection top

Agilent Xcalibur Gemini ultra diffractometer with Atlas detector	2382 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1769 reflections with I > 2σ(I)
T_min = 0.88, T_max = 0.91	R_int = 0.048
8663 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.100	Δρ_max = 0.16 e Å⁻³
S = 1.03	Δρ_min = −0.17 e Å⁻³
2382 reflections	Absolute structure: Flack (1983), with 991 Friedel pairs
169 parameters	Absolute structure parameter: −0.18 (9)
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cl1	0.87007 (10)	0.98698 (7)	0.87968 (5)	0.0705 (3)
O1	1.1714 (3)	1.01909 (17)	0.36679 (14)	0.0651 (6)
N1	1.0171 (3)	0.99976 (18)	0.52972 (14)	0.0456 (5)
C1	1.1228 (3)	1.1295 (2)	0.36948 (19)	0.0449 (6)
C2	1.1680 (4)	1.1989 (2)	0.2958 (2)	0.0510 (7)
H2	1.2327	1.1705	0.2462	0.061*
C3	1.1167 (4)	1.3109 (2)	0.29627 (19)	0.0498 (7)
H3	1.1449	1.3561	0.2454	0.060*
C4	1.0248 (3)	1.3579 (2)	0.36974 (19)	0.0451 (7)
C5	0.9829 (3)	1.2883 (2)	0.44320 (19)	0.0421 (6)
H5	0.9215	1.3181	0.4934	0.050*
C6	1.0296 (3)	1.1738 (2)	0.44475 (18)	0.0395 (6)
C7	0.9729 (4)	1.4803 (2)	0.3692 (2)	0.0653 (8)
H7A	0.8860	1.4932	0.4162	0.098*
H7B	0.9261	1.4996	0.3092	0.098*
H7C	1.0733	1.5263	0.3818	0.098*
C8	0.9758 (3)	1.1045 (2)	0.52278 (19)	0.0458 (7)
H8	0.9087	1.1370	0.5697	0.055*
C9	0.9585 (3)	0.9368 (2)	0.6085 (2)	0.0446 (7)
C10	0.9508 (3)	0.9850 (2)	0.69650 (18)	0.0459 (6)
H10	0.9883	1.0589	0.7055	0.055*
C11	0.8874 (4)	0.9232 (2)	0.77061 (19)	0.0493 (7)
C12	0.8366 (4)	0.8127 (3)	0.7589 (2)	0.0596 (8)
H12	0.7943	0.7710	0.8089	0.071*
C13	0.8498 (4)	0.7652 (2)	0.6719 (2)	0.0593 (8)
H13	0.8168	0.6901	0.6644	0.071*
C14	0.9102 (3)	0.8243 (2)	0.5945 (2)	0.0503 (7)
C15	0.9174 (4)	0.7697 (2)	0.5002 (2)	0.0680 (9)
H15A	1.0351	0.7715	0.4773	0.102*
H15B	0.8427	0.8099	0.4579	0.102*
H15C	0.8791	0.6927	0.5050	0.102*
H1	1.136 (5)	0.993 (3)	0.418 (3)	0.102*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0837 (5)	0.0789 (6)	0.0487 (5)	0.0012 (4)	0.0059 (4)	0.0083 (4)
O1	0.0850 (14)	0.0494 (12)	0.0608 (14)	0.0107 (11)	0.0181 (11)	−0.0039 (11)
N1	0.0509 (12)	0.0429 (12)	0.0430 (13)	−0.0007 (12)	−0.0008 (10)	0.0014 (11)
C1	0.0489 (14)	0.0421 (14)	0.0439 (17)	−0.0003 (12)	0.0010 (14)	−0.0065 (13)
C2	0.0581 (17)	0.0534 (17)	0.0414 (16)	−0.0070 (14)	0.0103 (14)	−0.0092 (14)
C3	0.0590 (16)	0.0519 (16)	0.0386 (16)	−0.0127 (16)	0.0026 (14)	0.0014 (13)
C4	0.0463 (14)	0.0429 (14)	0.0460 (18)	−0.0033 (12)	−0.0052 (13)	0.0036 (13)
C5	0.0442 (14)	0.0442 (14)	0.0378 (16)	−0.0006 (12)	0.0034 (12)	−0.0058 (12)
C6	0.0409 (13)	0.0416 (14)	0.0360 (16)	−0.0039 (12)	−0.0008 (12)	−0.0009 (12)
C7	0.0764 (19)	0.0512 (16)	0.068 (2)	0.0039 (16)	0.0027 (17)	0.0091 (17)
C8	0.0445 (15)	0.0480 (15)	0.0447 (18)	−0.0003 (13)	0.0003 (13)	−0.0012 (13)
C9	0.0411 (14)	0.0421 (14)	0.0505 (19)	0.0006 (11)	−0.0003 (13)	0.0066 (13)
C10	0.0464 (14)	0.0417 (13)	0.0497 (17)	−0.0017 (13)	−0.0003 (12)	0.0056 (14)
C11	0.0475 (16)	0.0528 (16)	0.0475 (18)	0.0044 (14)	0.0002 (14)	0.0111 (13)
C12	0.0596 (19)	0.0546 (19)	0.064 (2)	−0.0002 (15)	0.0067 (15)	0.0199 (16)
C13	0.0618 (19)	0.0399 (15)	0.076 (2)	−0.0021 (14)	0.0013 (17)	0.0095 (16)
C14	0.0469 (16)	0.0437 (15)	0.060 (2)	0.0048 (13)	−0.0010 (14)	0.0052 (14)
C15	0.075 (2)	0.0530 (17)	0.076 (2)	−0.0040 (16)	0.0029 (17)	−0.0109 (17)

Geometric parameters (Å, º) top

Cl1—C11	1.742 (3)	C7—H7B	0.9600
O1—C1	1.361 (3)	C7—H7C	0.9600
O1—H1	0.84 (4)	C8—H8	0.9300
N1—C8	1.284 (3)	C9—C10	1.387 (4)
N1—C9	1.426 (3)	C9—C14	1.397 (3)
C1—C2	1.383 (4)	C10—C11	1.379 (3)
C1—C6	1.396 (3)	C10—H10	0.9300
C2—C3	1.383 (4)	C11—C12	1.376 (4)
C2—H2	0.9300	C12—C13	1.372 (4)
C3—C4	1.384 (4)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.392 (4)
C4—C5	1.376 (3)	C13—H13	0.9300
C4—C7	1.503 (4)	C14—C15	1.501 (4)
C5—C6	1.403 (3)	C15—H15A	0.9600
C5—H5	0.9300	C15—H15B	0.9600
C6—C8	1.448 (3)	C15—H15C	0.9600
C7—H7A	0.9600

C1—O1—H1	104 (3)	N1—C8—H8	118.8
C8—N1—C9	119.3 (2)	C6—C8—H8	118.8
O1—C1—C2	118.8 (2)	C10—C9—C14	120.8 (2)
O1—C1—C6	121.5 (2)	C10—C9—N1	121.2 (2)
C2—C1—C6	119.7 (2)	C14—C9—N1	117.9 (2)
C1—C2—C3	119.7 (3)	C11—C10—C9	119.8 (2)
C1—C2—H2	120.2	C11—C10—H10	120.1
C3—C2—H2	120.2	C9—C10—H10	120.1
C2—C3—C4	122.3 (2)	C12—C11—C10	120.7 (3)
C2—C3—H3	118.9	C12—C11—Cl1	120.1 (2)
C4—C3—H3	118.9	C10—C11—Cl1	119.3 (2)
C5—C4—C3	117.4 (2)	C13—C12—C11	118.7 (3)
C5—C4—C7	121.3 (2)	C13—C12—H12	120.6
C3—C4—C7	121.3 (2)	C11—C12—H12	120.6
C4—C5—C6	122.1 (2)	C12—C13—C14	122.9 (3)
C4—C5—H5	118.9	C12—C13—H13	118.6
C6—C5—H5	118.9	C14—C13—H13	118.6
C1—C6—C5	118.7 (2)	C13—C14—C9	117.0 (3)
C1—C6—C8	122.1 (2)	C13—C14—C15	121.0 (2)
C5—C6—C8	119.2 (2)	C9—C14—C15	122.0 (3)
C4—C7—H7A	109.5	C14—C15—H15A	109.5
C4—C7—H7B	109.5	C14—C15—H15B	109.5
H7A—C7—H7B	109.5	H15A—C15—H15B	109.5
C4—C7—H7C	109.5	C14—C15—H15C	109.5
H7A—C7—H7C	109.5	H15A—C15—H15C	109.5
H7B—C7—H7C	109.5	H15B—C15—H15C	109.5
N1—C8—C6	122.5 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C9–C14 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84 (4)	1.84 (4)	2.629 (3)	154 (4)
C7—H7C···Cg1ⁱ	0.96	2.91	3.767 (3)	149

Symmetry code: (i) x+1/2, −y+5/2, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C9–C14 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84 (4)	1.84 (4)	2.629 (3)	154 (4)
C7—H7C···Cg1ⁱ	0.96	2.91	3.767 (3)	149

Symmetry code: (i) x+1/2, −y+5/2, −z+1.

Acknowledgements

The author acknowledges Lishui University for financial support.

References

Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England. Google Scholar
Ebrahimipour, S. Y., Mague, J. T., Akbari, A. & Takjoo, R. (2012). J. Mol. Struct. 1028, 148–155. Google Scholar
Fan, C.-B., Wang, X.-M., Ding, P., Wang, J.-J., Liang, Z.-Q. & Tao, X.-T. (2012). Dyes Pigm. 95, 757–767. Web of Science CSD CrossRef CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siddiqui, J. I., Iqbal, A., Ahmad, S. & Weaver, G. W. (2006). Molecules, 11, 206–211. Web of Science CrossRef PubMed CAS Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 8| August 2013| Page o1349

doi:10.1107/S1600536813019454

Open

access