Barium cobaltites are interesting materials because of a broad range of properties (magnetic, catalytic, electronic). Such properties are tightly connected to the structure type (so called hexagonal vs. cubic perovskite compounds) and compositions of the compounds. By the latter, different oxidation states of the cobalt ions can be assessed, which give rise to the various properties. In our recent research we found three new modifications of barium cobaltitets which have been so far unknown in this system. Additionally, those compounds can be modified by means of topochemical fluorination reactions. Within this proposal we aim to investigate nuclear (ordering of anion vacancies and structural distortions) and magnetic structures of such compounds, and the influence of composition and vacancy order on the spin states and magnetic properties of the cobalt ions.