DOI: dx.doi.org/10.19261/cjm.2013.08(2).01 Graphical Abstract: As a result of the comparative study of axial ligand orientation towards the equatorial plane in α - dioximates Co (III) obtained by us and those described in the specialized literature (found in Cambridge Crystallographic Data Centre) showed that the external anions and solvent molecules contribute to the orientation of axial ligands as selenourea and thiourea. For aniline and sulphanilamide ligands, is more convenient the parallel orientation to form π-π interactions between the aromatic rings of ligands and the metallocycle of equatorial plane.