organic compounds
4-Chloro-2-[(E)-(4-fluorophenyl)iminomethyl]phenol
aCollege of Mathematics and Physics, Lanzhou Jiaotong University, Lanzhou 730070, People's Republic of China
*Correspondence e-mail: fengtj707@126.com
In the title Schiff base molecule, C13H9ClFNO, the benzene rings are twisted slightly with respect to each other, making a dihedral angle of 7.92 (2)°. An intramolecular O—H⋯N hydrogen bond occurs. In the crystal, an infinite chain is formed along the c-axis direction by π–π stacking interactions between the phenyl rings and the six-membered hydrogen-bonded ring of neighboring Schiff base ligands [centroid–centroid distances of 3.698 (2) and 3.660 (3) Å]. Neighboring chains are linked into a three-dimensional supramolecular structure by C—H⋯O and C—H⋯F hydrogen bonds.
CCDC reference: 975729
Related literature
For the coordination modes of Schiff base ligands with transition metals, see: Ebrahimipour et al. (2012); Guo et al. (2013). For the biological activity of Schiff base ligands, see: Sawada et al. (2001); Ma et al. (2013); Siddiqui et al. (2006).
Experimental
Crystal data
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Data collection: CrysAlis PRO (Agilent, 2011); cell 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: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
Supporting information
CCDC reference: 975729
https://doi.org/10.1107/S1600536813033278/zl2572sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813033278/zl2572Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536813033278/zl2572Isup3.cml
Title compound was prepared by the condensation of 5-chlorosalicylaldehyde (0.783 g, 5 mmol) and 4-fluoroaniline (0.556 g, 5 mmol) in ethanol (15 ml) as the reaction medium. Glacial acetic acid (0.4 ml) was added and the solution was heated under reflux for 5 h and then allowed to cool to room temperature. The yellow precipitate was recrystallized from ethanol to give the title compound as straw yellow crystals. Yield 0.20 g (80%). [m.p. 361–363 K; IR (KBr, cm-1): 1637(s), 1560(m), 1508(w), 1460(w), 1392(w), 1324(w), 1288(w), 1210(w), 1120(w), 1054(w), 982(w), 932(w), 876(w), 810(w), 747(w), 709(w), 675(w), 564(w), 511(w); 1H NMR (CDCl3, δ, p.p.m.) 13.11 (s, 1H), 8.55 (s, 1H), 6.99–7.39 (m, 7H); 13C NMR (CDCl3, δ, p.p.m.) 161.1, 161.0, 160.7, 159.6, 144.2, 144.1, 133.0, 131.2, 123.8, 122.7, 122.6, 119.9, 118.9, 116.5, 116.2].
H atoms were fixed geometrically and treated as riding with O—H = 0.82 Å (hydroxy) and C—H = 0.93 Å, Uiso(H) = 1.2 Ueq(C) for aromatic H atoms and Uiso(H) = 1.5 Ueq(O) for the hydroxy H atom. The hightest residual electron density peak is located 0.91 Å from H1 and the deepest hole is located 0.91 Å from C13.
Schiff bases are considered important compounds because of their wide range of biological activities, and also because of their use as ligands in conjunction with transition metals. Schiff base ligands usually coordinate to a metal ion through the imine nitrogen atom, but coordination via other functional groups, e.g. through oxygen or carbon, has also been reported (Ebrahimipour et al., 2012; Guo et al., 2013).
derived from salicyladehyde and fluoroaniline, specifically, have been considered as potential pharmaceutically interesting compounds as several of the members of this family of molecules have shown antitumor, antimicrobial or antiviral activities (Sawada et al., 2001; Ma et al., 2013; Siddiqui et al., 2006). As an extension of our work on the structural characterization of Schiff base compounds, the solid state structure of the title compound is reported.The molecular structure of the title compound shows an E configuration, with a C8—N1=C7—C1 torsion angle of 178.33 (2) °. The bond distance of N1=C7 at 1.276 (3) Å is a typical double bond. It is noteworthy that the H1 atom bonded to O1 is involved in an O1—H1···N1 intramolecular hydrogen bond, which results in the formation of a six-membered ring (Table 1). The dihedral angle between the two planes of the chlorophenol ring and fluorphenyl ring is 7.92 (2) °. An infinite chain is formed by two types of π-π stacking interactions between the phenyl rings (C1—C6 and C8—C13) and the six-membered hydrogen bonded ring (C1/C2/O1/H1/N1/C7) of neighboring Schiff base ligands, with centroid–centroid distances of 3.698 (2) and 3.660 (3) Å, respectively and interplanar spacings of 3.395 (2) Å (Fig. 2a). Finally, neighboring chains are linked into a three-dimensional supramolecular structure by weak C—H···O and C—H···F hydrogen bonding interactions (Fig. 2 b, Table 1).
For the coordination modes of Schiff base ligands with transition metals, see: Ebrahimipour et al. (2012); Guo et al. (2013). For the biological activity of Schiff base ligands, see: Sawada et al. (2001); Ma et al. (2013); Siddiqui et al. (2006).
Data collection: CrysAlis PRO (Agilent, 2011); cell
CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C13H9ClFNO | F(000) = 512 |
Mr = 249.66 | Dx = 1.484 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3100 reflections |
a = 4.5140 (9) Å | θ = 1.7–26.0° |
b = 20.560 (4) Å | µ = 0.34 mm−1 |
c = 12.0712 (19) Å | T = 293 K |
β = 94.153 (16)° | Block, yellow |
V = 1117.4 (3) Å3 | 0.34 × 0.27 × 0.22 mm |
Z = 4 |
Agilent Xcalibur (Eos, Gemini) diffractometer | 2016 independent reflections |
Radiation source: fine-focus sealed tube | 1143 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
ω scans | θmax = 25.2°, θmin = 2.6° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | h = −5→5 |
Tmin = 0.908, Tmax = 0.942 | k = −23→24 |
6481 measured reflections | l = −14→14 |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0516P)2] where P = (Fo2 + 2Fc2)/3 |
2016 reflections | (Δ/σ)max < 0.001 |
155 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C13H9ClFNO | V = 1117.4 (3) Å3 |
Mr = 249.66 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.5140 (9) Å | µ = 0.34 mm−1 |
b = 20.560 (4) Å | T = 293 K |
c = 12.0712 (19) Å | 0.34 × 0.27 × 0.22 mm |
β = 94.153 (16)° |
Agilent Xcalibur (Eos, Gemini) diffractometer | 2016 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 1143 reflections with I > 2σ(I) |
Tmin = 0.908, Tmax = 0.942 | Rint = 0.065 |
6481 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.19 e Å−3 |
2016 reflections | Δρmin = −0.23 e Å−3 |
155 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2601 (7) | 0.22941 (16) | 0.7977 (3) | 0.0364 (8) | |
C2 | 0.1287 (7) | 0.22602 (17) | 0.6887 (3) | 0.0409 (8) | |
C3 | −0.0847 (8) | 0.17908 (18) | 0.6617 (3) | 0.0485 (10) | |
H3 | −0.1728 | 0.1772 | 0.5897 | 0.058* | |
C4 | −0.1685 (8) | 0.13523 (18) | 0.7395 (3) | 0.0480 (9) | |
H4 | −0.3112 | 0.1038 | 0.7202 | 0.058* | |
C5 | −0.0384 (8) | 0.13834 (17) | 0.8465 (3) | 0.0462 (9) | |
C6 | 0.1714 (7) | 0.18464 (16) | 0.8761 (3) | 0.0456 (9) | |
H6 | 0.2552 | 0.1863 | 0.9488 | 0.055* | |
C7 | 0.4848 (7) | 0.27750 (17) | 0.8303 (3) | 0.0420 (9) | |
H7 | 0.5699 | 0.2772 | 0.9028 | 0.050* | |
C8 | 0.7834 (7) | 0.36833 (16) | 0.7949 (3) | 0.0380 (8) | |
C9 | 0.8940 (7) | 0.37974 (17) | 0.9038 (3) | 0.0477 (9) | |
H9 | 0.8310 | 0.3540 | 0.9610 | 0.057* | |
C10 | 1.0968 (8) | 0.42908 (17) | 0.9277 (3) | 0.0517 (10) | |
H10 | 1.1698 | 0.4370 | 1.0005 | 0.062* | |
C11 | 1.1880 (8) | 0.46601 (17) | 0.8424 (3) | 0.0487 (9) | |
C12 | 1.0866 (8) | 0.45657 (18) | 0.7349 (3) | 0.0524 (10) | |
H12 | 1.1526 | 0.4824 | 0.6785 | 0.063* | |
C13 | 0.8819 (8) | 0.40728 (17) | 0.7116 (3) | 0.0494 (10) | |
H13 | 0.8093 | 0.4002 | 0.6385 | 0.059* | |
Cl1 | −0.1447 (3) | 0.08228 (5) | 0.94489 (9) | 0.0769 (4) | |
F1 | 1.3866 (5) | 0.51483 (10) | 0.86620 (19) | 0.0767 (7) | |
N1 | 0.5694 (6) | 0.32018 (13) | 0.7626 (2) | 0.0407 (7) | |
O1 | 0.2061 (6) | 0.26776 (13) | 0.60954 (19) | 0.0573 (7) | |
H1 | 0.3290 | 0.2937 | 0.6366 | 0.086* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0361 (18) | 0.039 (2) | 0.0332 (19) | 0.0018 (16) | −0.0011 (15) | −0.0019 (16) |
C2 | 0.044 (2) | 0.043 (2) | 0.035 (2) | −0.0010 (17) | 0.0013 (16) | −0.0047 (17) |
C3 | 0.052 (2) | 0.054 (2) | 0.038 (2) | 0.0012 (19) | −0.0047 (18) | −0.0142 (19) |
C4 | 0.048 (2) | 0.044 (2) | 0.051 (2) | −0.0036 (18) | 0.0013 (19) | −0.0134 (19) |
C5 | 0.053 (2) | 0.041 (2) | 0.044 (2) | −0.0051 (18) | 0.0023 (18) | −0.0012 (17) |
C6 | 0.051 (2) | 0.048 (2) | 0.037 (2) | 0.0005 (18) | −0.0034 (17) | −0.0033 (18) |
C7 | 0.0398 (19) | 0.046 (2) | 0.039 (2) | 0.0023 (17) | −0.0052 (16) | −0.0055 (18) |
C8 | 0.0378 (19) | 0.036 (2) | 0.039 (2) | 0.0013 (15) | −0.0008 (16) | −0.0005 (17) |
C9 | 0.052 (2) | 0.048 (2) | 0.043 (2) | −0.0075 (18) | 0.0015 (18) | −0.0019 (18) |
C10 | 0.059 (2) | 0.049 (2) | 0.045 (2) | −0.0026 (19) | −0.0100 (19) | −0.0030 (19) |
C11 | 0.045 (2) | 0.042 (2) | 0.058 (3) | −0.0080 (17) | −0.0024 (19) | −0.004 (2) |
C12 | 0.056 (2) | 0.049 (2) | 0.053 (2) | −0.005 (2) | 0.007 (2) | 0.0058 (19) |
C13 | 0.052 (2) | 0.053 (2) | 0.042 (2) | 0.0011 (19) | −0.0058 (18) | 0.0001 (19) |
Cl1 | 0.0965 (9) | 0.0668 (8) | 0.0659 (7) | −0.0274 (6) | −0.0031 (6) | 0.0137 (6) |
F1 | 0.0852 (16) | 0.0563 (15) | 0.0870 (17) | −0.0318 (13) | −0.0043 (13) | −0.0019 (13) |
N1 | 0.0397 (16) | 0.0414 (17) | 0.0407 (17) | −0.0025 (14) | 0.0010 (13) | −0.0040 (15) |
O1 | 0.0689 (19) | 0.0628 (18) | 0.0385 (14) | −0.0163 (14) | −0.0068 (13) | 0.0018 (14) |
C1—C6 | 1.400 (4) | C8—C13 | 1.384 (4) |
C1—C2 | 1.406 (4) | C8—C9 | 1.392 (4) |
C1—C7 | 1.450 (4) | C8—N1 | 1.418 (4) |
C2—O1 | 1.349 (4) | C9—C10 | 1.383 (5) |
C2—C3 | 1.385 (4) | C9—H9 | 0.9300 |
C3—C4 | 1.374 (5) | C10—C11 | 1.366 (5) |
C3—H3 | 0.9300 | C10—H10 | 0.9300 |
C4—C5 | 1.381 (5) | C11—C12 | 1.359 (5) |
C4—H4 | 0.9300 | C11—F1 | 1.362 (4) |
C5—C6 | 1.372 (4) | C12—C13 | 1.386 (5) |
C5—Cl1 | 1.747 (4) | C12—H12 | 0.9300 |
C6—H6 | 0.9300 | C13—H13 | 0.9300 |
C7—N1 | 1.276 (4) | O1—H1 | 0.8200 |
C7—H7 | 0.9300 | ||
C6—C1—C2 | 118.6 (3) | C13—C8—C9 | 118.5 (3) |
C6—C1—C7 | 119.6 (3) | C13—C8—N1 | 116.9 (3) |
C2—C1—C7 | 121.8 (3) | C9—C8—N1 | 124.6 (3) |
O1—C2—C3 | 119.2 (3) | C10—C9—C8 | 120.5 (3) |
O1—C2—C1 | 121.2 (3) | C10—C9—H9 | 119.8 |
C3—C2—C1 | 119.5 (3) | C8—C9—H9 | 119.8 |
C4—C3—C2 | 121.2 (3) | C11—C10—C9 | 118.8 (3) |
C4—C3—H3 | 119.4 | C11—C10—H10 | 120.6 |
C2—C3—H3 | 119.4 | C9—C10—H10 | 120.6 |
C3—C4—C5 | 119.3 (3) | C12—C11—F1 | 118.5 (3) |
C3—C4—H4 | 120.4 | C12—C11—C10 | 122.8 (4) |
C5—C4—H4 | 120.4 | F1—C11—C10 | 118.7 (3) |
C6—C5—C4 | 121.0 (3) | C11—C12—C13 | 118.1 (4) |
C6—C5—Cl1 | 119.9 (3) | C11—C12—H12 | 120.9 |
C4—C5—Cl1 | 119.1 (3) | C13—C12—H12 | 120.9 |
C5—C6—C1 | 120.4 (3) | C8—C13—C12 | 121.3 (3) |
C5—C6—H6 | 119.8 | C8—C13—H13 | 119.3 |
C1—C6—H6 | 119.8 | C12—C13—H13 | 119.3 |
N1—C7—C1 | 122.1 (3) | C7—N1—C8 | 122.3 (3) |
N1—C7—H7 | 119.0 | C2—O1—H1 | 109.5 |
C1—C7—H7 | 119.0 |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O1i | 0.93 | 2.69 | 3.569 (4) | 158 |
C10—H10···F1ii | 0.93 | 2.67 | 3.481 (4) | 147 |
O1—H1···N1 | 0.82 | 1.88 | 2.613 (3) | 148 |
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+3, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O1i | 0.93 | 2.69 | 3.569 (4) | 157.8 |
C10—H10···F1ii | 0.93 | 2.67 | 3.481 (4) | 146.5 |
O1—H1···N1 | 0.82 | 1.88 | 2.613 (3) | 147.5 |
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+3, −y+1, −z+2. |
Acknowledgements
The author acknowledges Lanzhou Jiaotong University for supporting this work.
References
Agilent (2011). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Ebrahimipour, S. Y., Mague, J. T., Akbari, A. & Takjoo, R. (2012). J. Mol. Struct. 1028, 148–155. Google Scholar
Guo, H. F., Zhao, X., Ma, D. Y., Xie, A. P. & Shen, W. B. (2013). Transition Met. Chem. 38, 299–305. Web of Science CSD CrossRef CAS Google Scholar
Ma, D. Y., Zhang, L. X., Rao, X. Y., Wu, T. L., Li, D. H. & Xie, X. Q. (2013). J. Coord. Chem. 66, 1486–1496. Web of Science CSD CrossRef CAS Google Scholar
Sawada, H., Yanagida, K., Inaba, Y., Sugiya, M., Kawase, T. & Tomita, T. (2001). Eur. Polym. J. 37, 1433–1439. Web of Science CrossRef CAS 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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Schiff bases are considered important compounds because of their wide range of biological activities, and also because of their use as ligands in conjunction with transition metals. Schiff base ligands usually coordinate to a metal ion through the imine nitrogen atom, but coordination via other functional groups, e.g. through oxygen or carbon, has also been reported (Ebrahimipour et al., 2012; Guo et al., 2013). Schiff bases derived from salicyladehyde and fluoroaniline, specifically, have been considered as potential pharmaceutically interesting compounds as several of the members of this family of molecules have shown antitumor, antimicrobial or antiviral activities (Sawada et al., 2001; Ma et al., 2013; Siddiqui et al., 2006). As an extension of our work on the structural characterization of Schiff base compounds, the solid state structure of the title compound is reported.
The molecular structure of the title compound shows an E configuration, with a C8—N1=C7—C1 torsion angle of 178.33 (2) °. The bond distance of N1=C7 at 1.276 (3) Å is a typical double bond. It is noteworthy that the H1 atom bonded to O1 is involved in an O1—H1···N1 intramolecular hydrogen bond, which results in the formation of a six-membered ring (Table 1). The dihedral angle between the two planes of the chlorophenol ring and fluorphenyl ring is 7.92 (2) °. An infinite chain is formed by two types of π-π stacking interactions between the phenyl rings (C1—C6 and C8—C13) and the six-membered hydrogen bonded ring (C1/C2/O1/H1/N1/C7) of neighboring Schiff base ligands, with centroid–centroid distances of 3.698 (2) and 3.660 (3) Å, respectively and interplanar spacings of 3.395 (2) Å (Fig. 2a). Finally, neighboring chains are linked into a three-dimensional supramolecular structure by weak C—H···O and C—H···F hydrogen bonding interactions (Fig. 2 b, Table 1).