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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2011 Jul 6;67(Pt 8):o1934. doi: 10.1107/S1600536811026122

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

Hoong-Kun Fun a,*,‡, Ching Kheng Quah a,§, S Viveka b, D J Madhukumar b, G K Nagaraja b
PMCID: PMC3212321  PMID: 22090978

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 ▶,b ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For standard bond-length data, see: Allen et al. (1987 ▶).graphic file with name e-67-o1934-scheme1.jpg

Experimental

Crystal data

  • C13H8Cl3NO

  • M r = 300.55

  • Monoclinic, Inline graphic

  • 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

  • Δρmax = 0.45 e Å−3

  • Δρmin = −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 ▶).

Supplementary Material

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

e-67-o1934-sup1.cif (16.6KB, cif)

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

e-67-o1934-Isup2.hkl (185.4KB, hkl)

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

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

Table 1. 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)
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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.

Refinement

H1O1 atom was located in a difference Fourier map and refined freely [O1–H1O1 = 0.79 (3) Å]. The remaining H atoms were positioned geometrically and refined using a riding model with C–H = 0.93 Å and Uiso(H) = 1.2 Ueq(C). The highest residual electron density peak and the deepest hole are located at 0.93 and 0.85 Å from Cl3, respectively.

Figures

Fig. 1.

Fig. 1.

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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
Mr = 300.55 Dx = 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
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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 Rint = 0.027
φ and ω scans θmax = 30.2°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009) h = −18→18
Tmin = 0.785, Tmax = 0.908 k = −9→9
10136 measured reflections l = −20→20
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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(Fo2) + (0.0489P)2 + 0.6136P] where P = (Fo2 + 2Fc2)/3
3782 reflections (Δ/σ)max < 0.001
167 parameters Δρmax = 0.45 e Å−3
0 restraints Δρmin = −0.44 e Å−3
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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.
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
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)*
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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)
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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)
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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)
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Footnotes

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

References

  1. Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  2. Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.
  3. Bhat, M. A., Imran, M., Khan, S. A. & Siddiqui, N. (2005). J. Pharm. Sci. 67, 151–159.
  4. Bruker (2009). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  5. Fun, H.-K., Quah, C. K., Viveka, S., Madhukumar, D. J. & Nagaraja, G. K. (2011a). Acta Cryst. E67, o1933. [DOI] [PMC free article] [PubMed]
  6. Fun, H.-K., Quah, C. K., Viveka, S., Madhukumar, D. J. & Prasad, D. J. (2011b). Acta Cryst. E67, o1932. [DOI] [PMC free article] [PubMed]
  7. Pandey, S. N., Lakshmi, V. S. & Pandey, A. (2003). Indian J. Pharm. Sci. 65, 213–222.
  8. Shapiro, H. K. (1998). Am. J. Ther. 5, 323–353. [DOI] [PubMed]
  9. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
  10. Spek, A. L. (2009). Acta Cryst. D65, 148–155. [DOI] [PMC free article] [PubMed]
  11. Venugopal, K. N. & Jayashree, B. S. (2008). Indian J. Pharm. Sci. 70, 88–91. [DOI] [PMC free article] [PubMed]
  12. Villar, R., Encio, I., Migliaccio, M., Gil, M. G. & Martinez-Merino, V. (2004). Bioorg. Med. Chem. 12, 963–968. [DOI] [PubMed]
  13. Wadher, S. J., Puranik, M. P., Karande, N. A. & Yeole, P. G. (2009). Int. J. PharmTech Res. 1, 22–33.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

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

e-67-o1934-sup1.cif (16.6KB, cif)

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

e-67-o1934-Isup2.hkl (185.4KB, hkl)

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

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography

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