A structural-thermochemical analysis of the Cambridge bank of structural data was performed according to specified number and types of intermolecular contacts. The TOPOS package and the SFERA and KONTAKT programs were used to analyze the structure of mononuclear barium molecular complexes containing completely screened barium atoms. Contacts between their molecules are formed by ligand hydrogen, carbon, and fluorine atoms only, whereas contacts of the type barium-barium or barium-any ligand atom of a neighboring molecule are absent. The enthalpies of vaporization of the selected complexes were estimated and a series of their volatility was established. The results were in agreement with the currently available experimental data.