Bond lengths in octahedral TiX(6)(2-) (X = F, Cl, Br, I) were optimized at the ab initio Hartree-Fock SCF level employing all electron MIDI and effective core potential valence basis sets of double-zeta quality, supplemented with diffuse functions. Energies resulting from these calculations were combined with those of X(2) (at optimal geometries) and Ti in order to determine energies of formation of TiX(6)(2-). The electron correlation was considered at the second-order Moller-Plesset level of theory to improve energetic characteristics. Vibrational frequencies were determined in the harmonic approximation and compared with available experimental data. Entropies, heat capacities, heats of formation, and free enthalpies of formation of gaseous TiX(6)(2-) in the standard state were evaluated by employing statistical thermodynamics. Electrostatic energies in hexahalogenotitanates were evaluated by the Ewald method adapted to complex ions. It was assumed for this purpose that the charge of each ion is a whole multiple of e and that net atomic charges in complex ions resulted from either various population analyses or a fit to the quantum mechanical electrostatic potential. The Coulombic energies are inversely dependent on the volume of the simplest structural unit and distances between interacting centers (Ti-cation). Theoretically revealed features conform with those available in the literature, mostly of experimental origin.