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Acta Cryst. (2009). E65, o512    [ doi:10.1107/S1600536809003924 ]

4-Chloro-2-[(E)-(2-chlorophenyl)iminomethyl]phenol

X. Zhang

Abstract top

The title compound, C13H9Cl2NO, was crystallized from a methanol solution of 5-chlorosalicylaldehyde and o-chloroaniline. The molecule displays a trans configuration with respect to the imine C=N double bond. The N atom is involved in an intramolecular O-H...N hydrogen bond. The two aromatic rings are essentially coplanar, the dihedral angle between them being 7.1 (1)°. A C-H...[pi] interaction is present in the crystal.

Comment top

The Schiff base containing some O and N atoms is a new important biological ligand and it shows some interesting biological properties, such as antibacterial, antiphlogistic, anticancer and high catalytic activities (Antony et al., 1999; Lumme & Elo et al., 1984; Yao et al., 1999), so the chemical behavior of the Schiff base has drawn our attention (Ueno et al., 2006). Our research emphasis is focused on the synthesis of the Schiff base. Then, a new crystal structure of the title compound, (I), is reported here.

The molecular structure of (I) are illustrated in Fig. 1. In the structure of (I), the whole molecule is essentially planar with a 7.1 (2)° dihedral angle between the two phenyl rings. The C1═N1 bond distance [1.277 (3)Å] is shorter than the standart 1.28Å value of C═N double bond, indicating a delocalization of π-electron density across the phenyl ring. In addition to the intramolecular O-H..N hydrogen bond, there is also an intermolecular C-H..π interaction (Table 1.)

Related literature top

For the biological properties of Schiff bases containing O and N atoms, see: Antony et al. (1999); Lumme & Elo (1984); Yao et al. (1999). For its chemical behaviour, see: Ueno et al. (2006). Cg1 is the centroid of C8–C13 phenyl ring.

Experimental top

A solution of 5-chlorosalicylaldehyde (0.1 mmol, 15.7 mg) in methanol (10 ml) was added dropwise to the methanol (10 ml) solution of o-chloroaniline (0.1 mmol, 12.8 mg) with stirring. The mixture was stirred at room temperature for one hour and then filtered. After allowing the filtrate to stand in air for 3 d, yellow block-shaped crystals of the title compound were formed in slow evaporation of the solvent. The crystals were collected, washed with methanol and dried in a vacuum desiccator using anhydrous CaCl2 (yield 60%).

Refinement top

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances 0.93Å and Uiso(H) = 1.2 Ueq(C) and O—H distances 0.82Å and Uiso(H) = 1.5 Ueq(O).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound with 30% probability ellipsoids. The dashed line represents hydrogen bond.
4-Chloro-2-[(E)-(2-chlorophenyl)iminomethyl]phenol top
Crystal data top
C13H9Cl2NOF(000) = 1088
Mr = 266.11Dx = 1.480 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3178 reflections
a = 7.2693 (13) Åθ = 2.9–26.3°
b = 13.0037 (19) ŵ = 0.52 mm−1
c = 25.2711 (16) ÅT = 298 K
V = 2388.8 (6) Å3Block, yellow
Z = 80.50 × 0.48 × 0.47 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer		2103 independent reflections
Radiation source: fine-focus sealed tube1496 reflections with I > 2σ(I)
graphiteRint = 0.041
φ and ω scansθmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Siemens, 1996)		h = −8→8
Tmin = 0.780, Tmax = 0.791k = −15→11
11102 measured reflectionsl = −30→29
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.099 w = 1/[σ2(Fo2) + (0.0287P)2 + 1.7853P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
2103 reflectionsΔρmax = 0.20 e Å−3
155 parametersΔρmin = −0.22 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0069 (6)
Crystal data top
C13H9Cl2NOV = 2388.8 (6) Å3
Mr = 266.11Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 7.2693 (13) ŵ = 0.52 mm−1
b = 13.0037 (19) ÅT = 298 K
c = 25.2711 (16) Å0.50 × 0.48 × 0.47 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer		2103 independent reflections
Absorption correction: multi-scan
(SADABS; Siemens, 1996)		1496 reflections with I > 2σ(I)
Tmin = 0.780, Tmax = 0.791Rint = 0.041
11102 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.099Δρmax = 0.20 e Å−3
S = 1.08Δρmin = −0.22 e Å−3
2103 reflectionsAbsolute structure: ?
155 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

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 > σ(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
xyzUiso*/Ueq
Cl10.07629 (12)1.13163 (6)1.12839 (3)0.0653 (3)
Cl20.41980 (14)0.79479 (6)0.83555 (3)0.0760 (3)
N10.3625 (3)0.96742 (15)0.90783 (8)0.0407 (5)
O10.2932 (4)0.81908 (14)0.97404 (8)0.0734 (7)
H10.32520.84570.94610.110*
C10.3120 (3)1.03135 (19)0.94334 (9)0.0396 (6)
H1A0.31321.10130.93570.048*
C20.2530 (3)0.99774 (18)0.99498 (9)0.0366 (6)
C30.2445 (4)0.89294 (19)1.00872 (10)0.0482 (7)
C40.1860 (4)0.8649 (2)1.05868 (11)0.0591 (8)
H40.18060.79561.06770.071*
C50.1357 (4)0.9376 (2)1.09521 (11)0.0519 (7)
H50.09720.91781.12880.062*
C60.1427 (4)1.04066 (19)1.08177 (10)0.0432 (6)
C70.1990 (4)1.07049 (19)1.03254 (10)0.0422 (6)
H70.20141.14001.02390.051*
C80.4229 (3)0.99867 (19)0.85743 (9)0.0393 (6)
C90.4587 (4)0.9228 (2)0.82003 (11)0.0462 (7)
C100.5255 (4)0.9469 (2)0.77026 (11)0.0588 (8)
H100.54870.89490.74590.071*
C110.5574 (4)1.0476 (3)0.75699 (12)0.0627 (8)
H110.60261.06410.72360.075*
C120.5224 (5)1.1235 (2)0.79298 (12)0.0635 (9)
H120.54391.19180.78390.076*
C130.4556 (4)1.1001 (2)0.84244 (11)0.0544 (7)
H130.43191.15290.86630.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0859 (6)0.0587 (5)0.0515 (4)0.0011 (4)0.0102 (4)−0.0135 (4)
Cl20.1089 (8)0.0424 (4)0.0766 (6)−0.0022 (4)0.0226 (5)−0.0113 (4)
N10.0478 (13)0.0375 (12)0.0367 (11)−0.0015 (10)−0.0029 (10)−0.0003 (10)
O10.128 (2)0.0355 (10)0.0562 (12)0.0156 (12)0.0259 (13)0.0034 (9)
C10.0434 (15)0.0330 (13)0.0424 (14)−0.0013 (11)−0.0043 (12)0.0023 (12)
C20.0385 (13)0.0335 (12)0.0377 (13)−0.0001 (10)−0.0036 (12)0.0011 (11)
C30.0614 (18)0.0379 (14)0.0452 (15)0.0094 (13)0.0001 (14)0.0028 (12)
C40.088 (2)0.0384 (15)0.0512 (16)0.0129 (15)0.0078 (16)0.0119 (14)
C50.0633 (19)0.0532 (17)0.0391 (14)0.0078 (14)0.0032 (14)0.0097 (13)
C60.0467 (16)0.0428 (15)0.0402 (14)0.0026 (12)−0.0029 (12)−0.0038 (12)
C70.0481 (16)0.0343 (13)0.0443 (15)−0.0037 (11)−0.0030 (12)−0.0001 (11)
C80.0390 (14)0.0436 (14)0.0353 (13)−0.0006 (12)−0.0059 (11)0.0024 (11)
C90.0472 (17)0.0435 (15)0.0479 (15)0.0012 (12)−0.0004 (13)−0.0024 (12)
C100.060 (2)0.068 (2)0.0478 (16)0.0039 (16)0.0083 (15)−0.0077 (15)
C110.063 (2)0.080 (2)0.0456 (16)−0.0032 (17)0.0071 (15)0.0107 (17)
C120.082 (2)0.0572 (18)0.0518 (17)−0.0089 (17)0.0014 (16)0.0151 (15)
C130.073 (2)0.0429 (15)0.0475 (16)−0.0042 (14)−0.0005 (15)0.0022 (13)
Geometric parameters (Å, °) top
Cl1—C61.738 (3)C5—H50.9300
Cl2—C91.733 (3)C6—C71.366 (3)
N1—C11.277 (3)C7—H70.9300
N1—C81.407 (3)C8—C91.391 (4)
O1—C31.347 (3)C8—C131.393 (4)
O1—H10.8200C9—C101.384 (4)
C1—C21.441 (3)C10—C111.371 (4)
C1—H1A0.9300C10—H100.9300
C2—C71.397 (3)C11—C121.367 (4)
C2—C31.408 (3)C11—H110.9300
C3—C41.381 (4)C12—C131.375 (4)
C4—C51.371 (4)C12—H120.9300
C4—H40.9300C13—H130.9300
C5—C61.383 (4)
C1—N1—C8122.5 (2)C6—C7—H7119.6
C3—O1—H1109.5C2—C7—H7119.6
N1—C1—C2121.6 (2)C9—C8—C13117.1 (2)
N1—C1—H1A119.2C9—C8—N1117.9 (2)
C2—C1—H1A119.2C13—C8—N1124.9 (2)
C7—C2—C3118.4 (2)C10—C9—C8121.5 (3)
C7—C2—C1119.6 (2)C10—C9—Cl2118.7 (2)
C3—C2—C1122.0 (2)C8—C9—Cl2119.8 (2)
O1—C3—C4119.2 (2)C11—C10—C9119.9 (3)
O1—C3—C2121.2 (2)C11—C10—H10120.1
C4—C3—C2119.6 (2)C9—C10—H10120.1
C5—C4—C3121.0 (3)C12—C11—C10119.7 (3)
C5—C4—H4119.5C12—C11—H11120.1
C3—C4—H4119.5C10—C11—H11120.1
C4—C5—C6119.5 (3)C11—C12—C13120.7 (3)
C4—C5—H5120.2C11—C12—H12119.6
C6—C5—H5120.2C13—C12—H12119.6
C7—C6—C5120.6 (2)C12—C13—C8121.2 (3)
C7—C6—Cl1120.5 (2)C12—C13—H13119.4
C5—C6—Cl1118.9 (2)C8—C13—H13119.4
C6—C7—C2120.7 (2)
C8—N1—C1—C2−179.1 (2)C1—C2—C7—C6−179.9 (2)
N1—C1—C2—C7180.0 (2)C1—N1—C8—C9−174.2 (2)
N1—C1—C2—C3−1.2 (4)C1—N1—C8—C138.1 (4)
C7—C2—C3—O1179.4 (3)C13—C8—C9—C100.6 (4)
C1—C2—C3—O10.6 (4)N1—C8—C9—C10−177.4 (3)
C7—C2—C3—C4−0.8 (4)C13—C8—C9—Cl2−179.5 (2)
C1—C2—C3—C4−179.6 (3)N1—C8—C9—Cl22.5 (3)
O1—C3—C4—C5179.8 (3)C8—C9—C10—C11−0.1 (4)
C2—C3—C4—C50.1 (5)Cl2—C9—C10—C11180.0 (2)
C3—C4—C5—C60.3 (5)C9—C10—C11—C12−0.2 (5)
C4—C5—C6—C70.1 (4)C10—C11—C12—C130.1 (5)
C4—C5—C6—Cl1179.4 (2)C11—C12—C13—C80.4 (5)
C5—C6—C7—C2−0.9 (4)C9—C8—C13—C12−0.7 (4)
Cl1—C6—C7—C2179.8 (2)N1—C8—C13—C12177.1 (3)
C3—C2—C7—C61.2 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.872.603 (3)147
C11—H11···Cg1i0.932.973.549 (3)122
Symmetry codes: (i) x−1/2, y, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.872.603 (3)147
C11—H11···Cg1i0.932.973.549 (3)122
Symmetry codes: (i) x−1/2, y, −z+1/2.
Acknowledgements top

This work was supported financially by research project No. 08JZ09 of the Phytochemistry Key Laboratory of Shaanxi Province.

references
References top

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Siemens (1996). SMART, SAINT and SADABS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Ueno, T., Yokoi, N., Unno, M., Matsui, T., Tokita, Y., Yamada, M., Ikeda-Saito, M., Nakajima, H. & Watanabe, Y. (2006). PNAS, 103, 9416–9421.

Yao, K. M., Li, N., Huang, Q. H., Shen, L.-F. & Yuan, H.-Z. (1999). Sci. China Ser. B Chem. 42, 53–61.