2-[(E)-(2,4,6-Trichloro­phen­yl)imino­meth­yl]phenol

doi:10.1107/S1600536811026122

Acta Crystallogr Sect E Struct Rep Online. 2011 August 1; 67(Pt 8): o1934.

Published online 2011 July 6. doi: 10.1107/S1600536811026122

PMCID: PMC3212321

2-[(E)-(2,4,6-Trichlorophenyl)iminomethyl]phenol

Hoong-Kun Fun,^a^*^‡ Ching Kheng Quah,^a^§ S. Viveka,^b D. J. Madhukumar,^b and G. K. Nagaraja^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia

^bDepartment of Chemistry, Mangalore University, Karnataka, India

Correspondence e-mail: hkfun/at/usm.my

^‡Thomson Reuters ResearcherID: A-3561-2009.

^§Thomson Reuters ResearcherID: A-5525-2009.

Received June 28, 2011; Accepted July 1, 2011.

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Abstract

The title molecule, C₁₃H₈Cl₃NO, exists in a trans configuration with respect to the C=N bond [1.278 (2) Å]. The benzene rings form a dihedral angle of 24.64 (11)°. The molecular structure is stabilized by an intramolecular O—H (...)

N hydrogen bond, which generates an S(6) ring motif. In the crystal, π–π stacking interactions [centroid–centroid distances = 3.6893 (14) Å] are observed.

Related literature

For general background to and the pharmacological activity of Schiff base compounds, see: Shapiro (1998

); Villar et al. (2004

); Venugopal & Jayashree (2008

); Pandey et al. (2003

); Bhat et al. (2005

); Wadher et al. (2009

). For related structures, see: Fun et al. (2011a

). For hydrogen-bond motifs, see: Bernstein et al. (1995

). For standard bond-length data, see: Allen et al. (1987

An external file that holds a picture, illustration, etc.
Object name is e-67-o1934-scheme1.jpg Object name is e-67-o1934-scheme1.jpg

Experimental

Crystal data

C₁₃H₈Cl₃NO
M _r = 300.55
Monoclinic,
a = 12.8847 (16) Å
b = 6.9505 (9) Å
c = 14.4265 (18) Å
β = 96.612 (2)°
V = 1283.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.70 mm⁻¹
T = 296 K
0.36 × 0.19 × 0.14 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T _min = 0.785, T _max = 0.908
10136 measured reflections
3782 independent reflections
2586 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.124
S = 1.02
3782 reflections
167 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Data collection: APEX2 (Bruker, 2009

); cell refinement: SAINT (Bruker, 2009

); data reduction: SAINT; 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 and PLATON (Spek, 2009

Table 1

Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811026122/lh5276sup1.cif

Click here to view.^{(17K, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811026122/lh5276Isup2.hkl

Click here to view.^{(185K, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811026122/lh5276Isup3.cml

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

Acknowledgments

HKF and CKQ thank Universiti Sains Malaysia for the Research University Grant (No. 1001/PFIZIK/811160).

supplementary crystallographic information

Comment

Schiff bases are the important compound owing to their wide range of biological activities and industrial application. The synthesis and structural research of Schiff bases are derived from aldehydes and amines bearing various alkyl and aryl N-substituents. Schiff base ligands may contain a variety of substituents with different electron-donating or electron-withdrawing groups and therefore may have interesting chemical properties. They have attracted particular interest due to their biological activities (Shapiro, 1998). They have been found to posses the pharmacological activities such as antimalarial, anticancer (Villar et al., 2004) antibacterial (Venugopal & Jayashree, 2008) antifungal (Pandey et al., 2003) antitubercular (Bhat et al., 2005), anti-inflammatory and antimicrobial (Wadher et al., 2009) properties.

In the title molecule (Fig. 1), the benzene rings (C1-C6 and C8-C13) form a dihedral angle of 24.64 (11)°. The title molecule exists in trans configuration with respect to the C7═N1 bond [C7═N1 = 1.278 (2) Å]. Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to related structures (Fun et al., 2011a,b). The molecular structure is stabilized by an intramolecular O1–H1O1···N1 hydrogen bond (Table 1) which generates a S(6) ring motif (Fig. 1, Bernstein et al., 1995).

In the crystal packing, π-π stacking interactions between the centroid of C1-C6 (Cg1) and C8-C13 (Cg2) benzene rings, with Cg1···Cg2ⁱ distance of 3.6893 (14) Å [symmetry code: (i) -x, -1/2+y, 3/2-z] are observed. No significant intermolecular hydrogen bonds are observed.

Experimental

A mixture of salicylaldehyde (0.01 mol) and 2,4,6-trichloroaniline (0.01 mol) was dissolved in a minimum amount of ethanol, followed by addition of 2 mL glacial acetic acid. The mixture was refluxed gently for 4-5 h. The reaction was monitored by TLC. After completion of the reaction, the mixture was poured into a beaker containing crushed ice. The precipitate obtained was filtered, dried and recrystallized from ethanol. Yield: 68%, m.p. 425-426 K.

Figures

Fig. 1.

The molecular structure of the title compound showing 30% probability displacement ellipsoids for non-H atoms. An intramolecular hydrogen bond is shown as a dashed line.

Crystal data

C₁₃H₈Cl₃NO	F(000) = 608
M_r = 300.55	D_x = 1.556 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3223 reflections
a = 12.8847 (16) Å	θ = 2.9–30.0°
b = 6.9505 (9) Å	µ = 0.70 mm⁻¹
c = 14.4265 (18) Å	T = 296 K
β = 96.612 (2)°	Block, yellow
V = 1283.4 (3) Å³	0.36 × 0.19 × 0.14 mm
Z = 4

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer	3782 independent reflections
Radiation source: fine-focus sealed tube	2586 reflections with I > 2σ(I)
graphite	R_int = 0.027
and ω scans	θ_max = 30.2°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −18→18
T_min = 0.785, T_max = 0.908	k = −9→9
10136 measured reflections	l = −20→20

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0489P)² + 0.6136P] where P = (F_o² + 2F_c²)/3
3782 reflections	(Δ/σ)_max < 0.001
167 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Special details

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)

	x	y	z	U_iso*/U_eq
Cl1	0.05175 (4)	0.34050 (9)	0.92951 (3)	0.05264 (16)
Cl2	0.44455 (4)	0.27949 (11)	0.84597 (5)	0.0669 (2)
Cl3	0.35845 (4)	0.16620 (13)	0.63858 (4)	0.0723 (2)
O1	−0.20343 (13)	0.2343 (3)	0.77771 (11)	0.0562 (4)
N1	−0.01212 (11)	0.2621 (2)	0.73161 (11)	0.0370 (3)
C1	0.13702 (14)	0.3001 (3)	0.84736 (13)	0.0368 (4)
C2	0.24358 (14)	0.3061 (3)	0.87539 (14)	0.0427 (4)
H2A	0.2685	0.3344	0.9369	0.051*
C3	0.31237 (14)	0.2693 (3)	0.81056 (15)	0.0428 (4)
C4	0.27450 (14)	0.2244 (3)	0.71929 (14)	0.0427 (4)
C5	0.16785 (14)	0.2223 (3)	0.69162 (13)	0.0408 (4)
H5A	0.1432	0.1931	0.6301	0.049*
C6	0.09726 (13)	0.2636 (3)	0.75513 (12)	0.0346 (4)
C7	−0.05235 (13)	0.3079 (3)	0.64944 (13)	0.0372 (4)
H7A	−0.0084	0.3437	0.6056	0.045*
C8	−0.16440 (14)	0.3060 (3)	0.62241 (14)	0.0387 (4)
C9	−0.20251 (16)	0.3408 (4)	0.52901 (15)	0.0514 (5)
H9A	−0.1558	0.3640	0.4857	0.062*
C10	−0.30845 (17)	0.3411 (4)	0.50043 (18)	0.0628 (7)
H10A	−0.3333	0.3623	0.4382	0.075*
C11	−0.37712 (17)	0.3093 (4)	0.56579 (19)	0.0638 (7)
H11A	−0.4486	0.3109	0.5471	0.077*
C12	−0.34176 (16)	0.2754 (4)	0.65778 (19)	0.0561 (6)
H12A	−0.3893	0.2549	0.7006	0.067*
C13	−0.23490 (15)	0.2716 (3)	0.68736 (15)	0.0430 (4)
H1O1	−0.142 (2)	0.238 (5)	0.787 (2)	0.077 (10)*

Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0521 (3)	0.0677 (4)	0.0399 (2)	0.0004 (3)	0.0130 (2)	−0.0002 (2)
Cl2	0.0322 (2)	0.0865 (5)	0.0786 (4)	−0.0046 (3)	−0.0083 (2)	0.0036 (3)
Cl3	0.0415 (3)	0.1152 (6)	0.0624 (4)	0.0192 (3)	0.0154 (2)	−0.0023 (4)
O1	0.0452 (8)	0.0715 (12)	0.0537 (9)	0.0035 (8)	0.0128 (7)	0.0064 (8)
N1	0.0303 (7)	0.0408 (9)	0.0400 (8)	0.0040 (6)	0.0037 (6)	−0.0019 (7)
C1	0.0366 (8)	0.0376 (10)	0.0365 (8)	−0.0005 (8)	0.0054 (7)	0.0016 (8)
C2	0.0388 (9)	0.0464 (12)	0.0407 (9)	−0.0037 (8)	−0.0044 (7)	0.0007 (8)
C3	0.0300 (8)	0.0448 (11)	0.0518 (11)	−0.0015 (8)	−0.0036 (7)	0.0060 (9)
C4	0.0319 (8)	0.0509 (12)	0.0459 (10)	0.0077 (8)	0.0070 (7)	0.0037 (9)
C5	0.0337 (8)	0.0502 (12)	0.0379 (9)	0.0065 (8)	0.0012 (7)	−0.0009 (8)
C6	0.0291 (7)	0.0349 (9)	0.0396 (9)	0.0009 (7)	0.0032 (6)	0.0000 (7)
C7	0.0309 (8)	0.0399 (10)	0.0411 (9)	0.0031 (7)	0.0049 (7)	−0.0029 (8)
C8	0.0305 (8)	0.0391 (10)	0.0460 (9)	0.0031 (7)	0.0020 (7)	−0.0049 (8)
C9	0.0404 (10)	0.0649 (15)	0.0473 (10)	0.0039 (10)	−0.0016 (8)	−0.0046 (10)
C10	0.0443 (11)	0.0808 (19)	0.0592 (13)	0.0061 (11)	−0.0114 (10)	−0.0079 (13)
C11	0.0352 (10)	0.0735 (18)	0.0790 (17)	0.0022 (11)	−0.0098 (10)	−0.0134 (14)
C12	0.0346 (9)	0.0597 (15)	0.0752 (15)	−0.0016 (10)	0.0109 (10)	−0.0075 (12)
C13	0.0360 (9)	0.0391 (11)	0.0544 (11)	0.0025 (8)	0.0072 (8)	−0.0047 (9)

Geometric parameters (Å, °)

Cl1—C1	1.7292 (19)	C5—H5A	0.9300
Cl2—C3	1.7222 (18)	C7—C8	1.452 (2)
Cl3—C4	1.726 (2)	C7—H7A	0.9300
O1—C13	1.345 (3)	C8—C13	1.399 (3)
O1—H1O1	0.79 (3)	C8—C9	1.401 (3)
N1—C7	1.278 (2)	C9—C10	1.380 (3)
N1—C6	1.411 (2)	C9—H9A	0.9300
C1—C2	1.387 (2)	C10—C11	1.383 (4)
C1—C6	1.393 (2)	C10—H10A	0.9300
C2—C3	1.384 (3)	C11—C12	1.373 (4)
C2—H2A	0.9300	C11—H11A	0.9300
C3—C4	1.386 (3)	C12—C13	1.394 (3)
C4—C5	1.386 (2)	C12—H12A	0.9300
C5—C6	1.393 (2)

C13—O1—H1O1	110 (2)	N1—C7—H7A	119.0
C7—N1—C6	120.55 (16)	C8—C7—H7A	119.0
C2—C1—C6	121.80 (17)	C13—C8—C9	119.42 (18)
C2—C1—Cl1	118.76 (14)	C13—C8—C7	121.61 (18)
C6—C1—Cl1	119.44 (13)	C9—C8—C7	118.97 (18)
C3—C2—C1	119.14 (17)	C10—C9—C8	120.8 (2)
C3—C2—H2A	120.4	C10—C9—H9A	119.6
C1—C2—H2A	120.4	C8—C9—H9A	119.6
C2—C3—C4	120.04 (17)	C9—C10—C11	119.0 (2)
C2—C3—Cl2	118.70 (15)	C9—C10—H10A	120.5
C4—C3—Cl2	121.26 (16)	C11—C10—H10A	120.5
C3—C4—C5	120.32 (18)	C12—C11—C10	121.3 (2)
C3—C4—Cl3	120.94 (15)	C12—C11—H11A	119.4
C5—C4—Cl3	118.73 (15)	C10—C11—H11A	119.4
C4—C5—C6	120.60 (17)	C11—C12—C13	120.4 (2)
C4—C5—H5A	119.7	C11—C12—H12A	119.8
C6—C5—H5A	119.7	C13—C12—H12A	119.8
C1—C6—C5	118.01 (16)	O1—C13—C12	118.5 (2)
C1—C6—N1	118.57 (16)	O1—C13—C8	122.39 (18)
C5—C6—N1	123.37 (16)	C12—C13—C8	119.1 (2)
N1—C7—C8	122.10 (17)

C6—C1—C2—C3	−1.9 (3)	C7—N1—C6—C1	151.17 (19)
Cl1—C1—C2—C3	178.45 (16)	C7—N1—C6—C5	−31.6 (3)
C1—C2—C3—C4	−0.9 (3)	C6—N1—C7—C8	179.28 (17)
C1—C2—C3—Cl2	179.37 (16)	N1—C7—C8—C13	6.2 (3)
C2—C3—C4—C5	2.1 (3)	N1—C7—C8—C9	−174.2 (2)
Cl2—C3—C4—C5	−178.18 (17)	C13—C8—C9—C10	−0.2 (4)
C2—C3—C4—Cl3	−176.72 (17)	C7—C8—C9—C10	−179.7 (2)
Cl2—C3—C4—Cl3	3.0 (3)	C8—C9—C10—C11	1.0 (4)
C3—C4—C5—C6	−0.5 (3)	C9—C10—C11—C12	−0.8 (4)
Cl3—C4—C5—C6	178.34 (16)	C10—C11—C12—C13	−0.3 (4)
C2—C1—C6—C5	3.4 (3)	C11—C12—C13—O1	−178.8 (2)
Cl1—C1—C6—C5	−176.92 (15)	C11—C12—C13—C8	1.1 (4)
C2—C1—C6—N1	−179.22 (18)	C9—C8—C13—O1	179.0 (2)
Cl1—C1—C6—N1	0.5 (3)	C7—C8—C13—O1	−1.5 (3)
C4—C5—C6—C1	−2.2 (3)	C9—C8—C13—C12	−0.9 (3)
C4—C5—C6—N1	−179.41 (19)	C7—C8—C13—C12	178.7 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···N1	0.79 (3)	1.94 (3)	2.633 (2)	146 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH5276).

References

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