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Acta Cryst. (2007). E63, o3944    [ doi:10.1107/S160053680704233X ]

2-[(2-Aminophenylimino)(phenyl)methyl]-4,6-dichlorophenol

W.-H. Li, F.-Q. Liu, X.-D. Zhao, J.-Y. Deng and B.-R. Hou

Abstract top

The title compound, C19H14Cl2N2O, a tridentate Schiff base, has been synthesized and structurally characterized by X-ray structure analysis. The hydroxy and imino groups are involved in a resonance-assisted O-H...N hydrogen bond [O...N = 2.502 (3) Å]. Intermolecular N-H...O hydrogen bonds further stabilize the crystal packing.

Comment top

In the title compound, (I), (Fig. 1), the atom N2 lies in the planes of imino-phenyl and hydroxy-phenyl groups. The dihedral angle formed by the two phenyls is 43.51 (7)°. The C7═N2 (1.298 (3) Å), C7—C14 (1.475 (4) Å) and O1—C19 (1.330 (3) Å) bond lengths are shorter than normal C═N (1.32 Å), C—C (1.54 Å) and O—C (1.44 Å) bonds (Allen et al., 1987). The C14—C19 bond length (1.424 (4) Å) is longer than a normal C═C bond (1.40 Å in benzene). These differences in bond lengths are related to a resonance-assisted hydrogen bond (RAHBA) acting between molecules with conjugated multiple π bonds (Gilli et al., 2000). Intermolecular N—H···O hydrogen bonds further stabilize the crystal packing. In the related 4-chlorophenyl compound similar resonance-assisted O—H···N hydrogen bonding was reported (Ai et al., 2006).

Related literature top

For related literature, see: Ai et al. (2006); Allen et al. (1987); Gilli et al. (2000).

Experimental top

4,6-Dichloro-2-hydroxybenzophenone was prepared via the Fries rearrangement of 3,5-dichlorophenyl benzoate. Then this ketone (26.7 g, 0.1 mol), o-phenylenediamine (10.8 g, 0.1 mol), piperidine (9.4 g, 0.11 mol), and triethylorthoformate (16 ml) were refluxed in anhydrous ethanol (100 ml) to give a red product of the mono-condensed Schiff base 2-[(2-aminophenylimino)-phenylmethyl]-4,6-dichlorophenol. The precipitated solid was collected by filtration and washed twice with hot methanol. Single crystals suitable for X-ray measurements were obtained by slow evaporation of absolute ethanol and acetic ether (2:1 v/v) at room temperature.

Refinement top

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with N—H = 0.86 Å, C—H = 0.93 Å and O—H = 0.85 Å, and with Uiso(H) = 1.2Ueq(C) for the aromatic H atoms or 1.2Ueq(parent) for the other atoms. H atoms were positioned geometrically (C—H = 0.93 Å) and allowed to ride on their parent atoms with Uiso(H) = 1.2 times Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001) and local programs.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. The packing of (I), viewed down the b axis.
2-[(2-Aminophenylimino)(phenyl)methyl]-4,6-dichlorophenol top
Crystal data top
C19H14Cl2N2OZ = 2
Mr = 357.22F000 = 368
Triclinic, P1Dx = 1.440 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.9833 (18) ÅCell parameters from 2933 reflections
b = 9.4191 (19) Åθ = 2.5–26.0º
c = 11.361 (2) ŵ = 0.40 mm−1
α = 66.61 (3)ºT = 293 (2) K
β = 72.87 (3)ºBlock, colourless
γ = 72.38 (3)º0.30 × 0.20 × 0.10 mm
V = 824.0 (4) Å3
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		3625 independent reflections
Radiation source: fine-focus sealed tube2801 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.012
T = 293(2) Kθmax = 27.1º
thin–slice ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −10→11
Tmin = 0.901, Tmax = 0.963k = −11→9
3854 measured reflectionsl = −14→14
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)] = 0.054H-atom parameters constrained
wR(F2) = 0.171  w = 1/[σ2(Fo2) + (0.0797P)2 + 0.556P]
where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max < 0.001
3625 reflectionsΔρmax = 0.31 e Å−3
217 parametersΔρmin = −0.30 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C19H14Cl2N2Oγ = 72.38 (3)º
Mr = 357.22V = 824.0 (4) Å3
Triclinic, P1Z = 2
a = 8.9833 (18) ÅMo Kα
b = 9.4191 (19) ŵ = 0.40 mm−1
c = 11.361 (2) ÅT = 293 (2) K
α = 66.61 (3)º0.30 × 0.20 × 0.10 mm
β = 72.87 (3)º
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		3625 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		2801 reflections with I > 2σ(I)
Tmin = 0.901, Tmax = 0.963Rint = 0.012
3854 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.054217 parameters
wR(F2) = 0.171H-atom parameters constrained
S = 1.13Δρmax = 0.31 e Å−3
3625 reflectionsΔρmin = −0.30 e Å−3
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 > 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
xyzUiso*/Ueq
Cl10.02655 (9)0.32831 (12)0.43610 (8)0.0610 (3)
Cl20.62563 (10)0.17475 (13)0.18588 (8)0.0667 (3)
O10.7144 (2)0.1622 (3)0.4170 (2)0.0484 (5)
H10.73760.20600.45990.058*
N10.9269 (3)−0.0348 (3)0.6999 (3)0.0603 (7)
H1A1.0099−0.10700.71980.072*
H1B0.8726−0.04100.65180.072*
N20.6616 (3)0.1981 (3)0.6334 (2)0.0402 (5)
C10.8814 (3)0.0902 (4)0.7449 (3)0.0465 (7)
C20.9686 (4)0.1012 (5)0.8227 (3)0.0604 (9)
H2B1.05920.02370.84260.072*
C30.9244 (5)0.2225 (5)0.8704 (4)0.0690 (11)
H3A0.98530.22630.92210.083*
C40.7907 (4)0.3402 (4)0.8434 (3)0.0585 (9)
H4A0.76130.42310.87600.070*
C50.7012 (4)0.3318 (4)0.7666 (3)0.0486 (7)
H5A0.61200.41110.74610.058*
C60.7427 (3)0.2074 (4)0.7199 (3)0.0399 (6)
C70.5084 (3)0.2380 (3)0.6407 (3)0.0374 (6)
C80.3940 (3)0.2836 (3)0.7510 (3)0.0361 (6)
C90.3843 (3)0.1752 (4)0.8777 (3)0.0430 (6)
H9A0.44200.07160.89240.052*
C100.2890 (4)0.2213 (4)0.9816 (3)0.0529 (8)
H10A0.28120.14831.06610.063*
C110.2051 (4)0.3761 (5)0.9603 (3)0.0561 (8)
H11A0.14410.40801.03080.067*
C120.2117 (4)0.4822 (4)0.8356 (3)0.0538 (8)
H12A0.15280.58540.82150.065*
C130.3049 (3)0.4373 (4)0.7306 (3)0.0469 (7)
H13A0.30830.50990.64600.056*
C140.4484 (3)0.2356 (3)0.5341 (3)0.0367 (6)
C150.2839 (3)0.2715 (4)0.5370 (3)0.0424 (6)
H15A0.21170.29140.60930.051*
C160.2297 (3)0.2773 (4)0.4349 (3)0.0444 (7)
C170.3345 (3)0.2457 (4)0.3270 (3)0.0444 (7)
H17A0.29620.24880.25820.053*
C180.4950 (3)0.2097 (4)0.3227 (3)0.0427 (6)
C190.5575 (3)0.2001 (3)0.4248 (3)0.0398 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0374 (4)0.0925 (7)0.0603 (5)−0.0136 (4)−0.0155 (3)−0.0289 (5)
Cl20.0573 (5)0.1012 (8)0.0515 (5)−0.0093 (5)−0.0022 (4)−0.0475 (5)
O10.0349 (10)0.0656 (14)0.0490 (11)−0.0030 (9)−0.0081 (9)−0.0294 (10)
N10.0488 (16)0.0594 (17)0.0722 (19)0.0062 (13)−0.0190 (14)−0.0297 (15)
N20.0346 (12)0.0504 (14)0.0392 (12)−0.0050 (10)−0.0101 (9)−0.0196 (11)
C10.0353 (14)0.0550 (18)0.0408 (15)−0.0114 (13)−0.0053 (12)−0.0077 (13)
C20.0439 (18)0.069 (2)0.063 (2)−0.0079 (16)−0.0256 (16)−0.0095 (18)
C30.064 (2)0.090 (3)0.063 (2)−0.032 (2)−0.0342 (18)−0.009 (2)
C40.064 (2)0.067 (2)0.060 (2)−0.0212 (17)−0.0187 (17)−0.0274 (17)
C50.0432 (16)0.0547 (18)0.0518 (17)−0.0080 (13)−0.0137 (13)−0.0206 (15)
C60.0327 (13)0.0526 (16)0.0330 (13)−0.0101 (12)−0.0069 (11)−0.0119 (12)
C70.0357 (14)0.0412 (15)0.0340 (13)−0.0052 (11)−0.0093 (11)−0.0117 (11)
C80.0317 (13)0.0468 (15)0.0352 (13)−0.0097 (11)−0.0090 (10)−0.0168 (12)
C90.0442 (15)0.0472 (16)0.0425 (15)−0.0092 (12)−0.0128 (12)−0.0176 (13)
C100.0483 (17)0.078 (2)0.0351 (14)−0.0207 (16)−0.0063 (13)−0.0179 (15)
C110.0426 (17)0.085 (3)0.0525 (18)−0.0109 (16)−0.0032 (14)−0.0417 (18)
C120.0418 (16)0.0587 (19)0.069 (2)−0.0003 (14)−0.0115 (15)−0.0374 (17)
C130.0403 (15)0.0511 (17)0.0438 (15)−0.0037 (13)−0.0096 (12)−0.0139 (13)
C140.0350 (13)0.0438 (15)0.0338 (13)−0.0083 (11)−0.0084 (11)−0.0144 (11)
C150.0330 (13)0.0555 (17)0.0352 (13)−0.0079 (12)−0.0052 (11)−0.0140 (13)
C160.0350 (14)0.0544 (17)0.0448 (15)−0.0132 (12)−0.0115 (12)−0.0126 (13)
C170.0470 (16)0.0543 (17)0.0360 (14)−0.0116 (13)−0.0126 (12)−0.0158 (13)
C180.0438 (15)0.0499 (16)0.0363 (14)−0.0092 (12)−0.0040 (12)−0.0198 (13)
C190.0344 (14)0.0439 (15)0.0371 (14)−0.0052 (11)−0.0068 (11)−0.0121 (12)
Geometric parameters (Å, °) top
Cl1—C161.738 (3)C7—C81.487 (4)
Cl2—C181.732 (3)C8—C131.390 (4)
O1—C191.330 (3)C8—C91.391 (4)
O1—H10.8500C9—C101.379 (4)
N1—C11.370 (4)C9—H9A0.9300
N1—H1A0.8600C10—C111.384 (5)
N1—H1B0.8600C10—H10A0.9300
N2—C71.298 (3)C11—C121.368 (5)
N2—C61.426 (3)C11—H11A0.9300
C1—C21.392 (5)C12—C131.379 (4)
C1—C61.407 (4)C12—H12A0.9300
C2—C31.358 (6)C13—H13A0.9300
C2—H2B0.9300C14—C151.405 (4)
C3—C41.381 (5)C14—C191.424 (4)
C3—H3A0.9300C15—C161.362 (4)
C4—C51.385 (4)C15—H15A0.9300
C4—H4A0.9300C16—C171.385 (4)
C5—C61.380 (4)C17—C181.368 (4)
C5—H5A0.9300C17—H17A0.9300
C7—C141.475 (4)C18—C191.393 (4)
C19—O1—H1109.1C8—C9—H9A120.0
C1—N1—H1A120.0C9—C10—C11120.1 (3)
C1—N1—H1B120.0C9—C10—H10A120.0
H1A—N1—H1B120.0C11—C10—H10A120.0
C7—N2—C6125.4 (2)C12—C11—C10120.1 (3)
N1—C1—C2120.4 (3)C12—C11—H11A120.0
N1—C1—C6122.1 (3)C10—C11—H11A120.0
C2—C1—C6117.4 (3)C11—C12—C13120.5 (3)
C3—C2—C1121.6 (3)C11—C12—H12A119.8
C3—C2—H2B119.2C13—C12—H12A119.8
C1—C2—H2B119.2C12—C13—C8120.0 (3)
C2—C3—C4121.2 (3)C12—C13—H13A120.0
C2—C3—H3A119.4C8—C13—H13A120.0
C4—C3—H3A119.4C15—C14—C19119.2 (2)
C3—C4—C5118.4 (3)C15—C14—C7120.8 (2)
C3—C4—H4A120.8C19—C14—C7120.0 (2)
C5—C4—H4A120.8C16—C15—C14120.5 (3)
C6—C5—C4121.0 (3)C16—C15—H15A119.8
C6—C5—H5A119.5C14—C15—H15A119.8
C4—C5—H5A119.5C15—C16—C17121.0 (3)
C5—C6—C1120.3 (3)C15—C16—Cl1120.5 (2)
C5—C6—N2123.4 (3)C17—C16—Cl1118.6 (2)
C1—C6—N2116.0 (3)C18—C17—C16119.4 (3)
N2—C7—C14117.3 (2)C18—C17—H17A120.3
N2—C7—C8123.0 (2)C16—C17—H17A120.3
C14—C7—C8119.7 (2)C17—C18—C19122.2 (3)
C13—C8—C9119.3 (3)C17—C18—Cl2119.1 (2)
C13—C8—C7120.7 (2)C19—C18—Cl2118.6 (2)
C9—C8—C7119.9 (2)O1—C19—C18120.0 (2)
C10—C9—C8120.0 (3)O1—C19—C14122.2 (2)
C10—C9—H9A120.0C18—C19—C14117.7 (2)
N1—C1—C2—C3−178.9 (3)C11—C12—C13—C8−0.4 (5)
C6—C1—C2—C3−1.6 (5)C9—C8—C13—C121.8 (4)
C1—C2—C3—C40.0 (6)C7—C8—C13—C12−173.3 (3)
C2—C3—C4—C50.3 (6)N2—C7—C14—C15177.6 (3)
C3—C4—C5—C61.2 (5)C8—C7—C14—C15−1.8 (4)
C4—C5—C6—C1−2.9 (5)N2—C7—C14—C19−3.8 (4)
C4—C5—C6—N2−175.6 (3)C8—C7—C14—C19176.8 (2)
N1—C1—C6—C5−179.8 (3)C19—C14—C15—C16−2.2 (4)
C2—C1—C6—C53.1 (4)C7—C14—C15—C16176.5 (3)
N1—C1—C6—N2−6.5 (4)C14—C15—C16—C171.1 (5)
C2—C1—C6—N2176.3 (3)C14—C15—C16—Cl1−177.8 (2)
C7—N2—C6—C5−40.2 (4)C15—C16—C17—C18−0.7 (5)
C7—N2—C6—C1146.7 (3)Cl1—C16—C17—C18178.2 (2)
C6—N2—C7—C14173.7 (2)C16—C17—C18—C191.5 (5)
C6—N2—C7—C8−6.8 (4)C16—C17—C18—Cl2−178.5 (2)
N2—C7—C8—C13113.4 (3)C17—C18—C19—O1178.9 (3)
C14—C7—C8—C13−67.2 (4)Cl2—C18—C19—O1−1.1 (4)
N2—C7—C8—C9−61.6 (4)C17—C18—C19—C14−2.6 (4)
C14—C7—C8—C9117.8 (3)Cl2—C18—C19—C14177.5 (2)
C13—C8—C9—C10−1.0 (4)C15—C14—C19—O1−178.7 (3)
C7—C8—C9—C10174.1 (3)C7—C14—C19—O12.7 (4)
C8—C9—C10—C11−1.1 (4)C15—C14—C19—C182.8 (4)
C9—C10—C11—C122.4 (5)C7—C14—C19—C18−175.8 (3)
C10—C11—C12—C13−1.7 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N20.851.872.502 (3)130
N1—H1A···O1i0.862.533.161 (4)131
N1—H1B···N20.862.452.765 (4)103
Symmetry codes: (i) −x+2, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N20.851.872.502 (3)130
N1—H1A···O1i0.862.533.161 (4)131
N1—H1B···N20.862.452.765 (4)103
Symmetry codes: (i) −x+2, −y, −z+1.
Acknowledgements top

The authors gratefully acknowledge the support of the China Postdoctoral Science Foundation and the Knowledge Innovation Project of the Chinese Academy of Science (grant No. KZXCX2-YW-210).

references
References top

Ai, X.-K., Bi, C.-F., Fan, Y.-H., Zhang, X. & He, X.-T. (2006). Acta Cryst. E62, o3475–o3476.

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.

Bruker (2001). SMART (Version 5.628) and SAINT (Version 6.45). Bruker AXS Inc., Madison, Wisconsin, USA.

Gilli, P., Bertolasi, V., Ferretti, V. & Gilli, G. (2000). J. Am. Chem. Soc. 122, 10405–10417.

Sheldrick, G. M. (2001). SHELXTL. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.