Bis[4-chloro-2-(quinolin-8-yliminomethyl)phenolato-κ3 N,N′,O]cobalt(III) trichloridomethanolcobaltate(II)

The reaction of 4-chloro-2-(quinolin-8-yliminomethyl)phenol (HClQP) with cobalt(II) dichloride hexahydrate in methanol/chloroform under solvothermal conditions yielded the title compound, [Co(C16H10ClN2O)2][CoCl3(CH3OH)]. The CoIII atom is six-coordinated in a slightly distorted octahedral geometry by four N atoms and two O atoms of two tridentate HClQP ligands, which are nearly perpendicular to each other, making a dihedral angle of 86.95°. The CoII atom is four-coordinated by three Cl atoms and one O atom from a methanol ligand in a distorted tetrahedral geometry. The crystal packing is consolidated by intermolecular O—H⋯Cl, C—H⋯Cl and C—H⋯O hydrogen bonds, forming a three-dimensional supramolecular structure, in which [CoIICl3(CH3OH)] anions are connected via O—H⋯Cl and C—H⋯Cl hydrogen bonds into centrosymmetric dimers. Neighboring cobalt(III) complexes form dimers through C—H⋯O hydrogen bonds, as well as π–π stacking [centroid–centroid distances = 3.30 (2) Å] between the planar quinoline systems of one HClQP ligand and the phenolate ring of another.

The reaction of 4-chloro-2-(quinolin-8-yliminomethyl)phenol (HClQP) with cobalt(II) dichloride hexahydrate in methanol/ chloroform under solvothermal conditions yielded the title compound, [Co(C 16 H 10 ClN 2 O) 2 ][CoCl 3 (CH 3 OH)]. The Co III atom is six-coordinated in a slightly distorted octahedral geometry by four N atoms and two O atoms of two tridentate HClQP ligands, which are nearly perpendicular to each other, making a dihedral angle of 86.95 . The Co II atom is fourcoordinated by three Cl atoms and one O atom from a methanol ligand in a distorted tetrahedral geometry. The crystal packing is consolidated by intermolecular O-HÁ Á ÁCl, C-HÁ Á ÁCl and C-HÁ Á ÁO hydrogen bonds, forming a threedimensional supramolecular structure, in which [Co II Cl 3 -(CH 3 OH)] anions are connected via O-HÁ Á ÁCl and C-HÁ Á ÁCl hydrogen bonds into centrosymmetric dimers. Neighboring cobalt(III) complexes form dimers through C-HÁ Á ÁO hydrogen bonds, as well asstacking [centroid-centroid distances = 3.30 (2) Å ] between the planar quinoline systems of one HClQP ligand and the phenolate ring of another.
Crystal structure refinement of the title complex revealed that half of the cobalt(II) of the starting material was oxidized complexes form dimers through C-H···O hydrogen bonds, as well as π-π stacking between the planar quinoline of one HClQP ligand and the phenol ring of another.

Preparation of 4-Chloro-2-(quinolin-8-yliminomethyl)-phenol (HClQP):
A mixture of 5-chloro-2-hydroxybenzaldehyde (1 mmol, 0.156 g) and 8-aminoquinoline (1 mmol, 0.144 g) in anhydrous ethanol (30 ml) was stirred for 3 h at 323 K and then was concentrated to ca 10 ml. Hexane was then added to the solution and it was allowed to cool down to room temperature. The orange precipitate that formed was filtered off,  The molecular structure showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Special details
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 F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 )
x y z U iso */U eq