Graphycal Abstract: The present study describes synthesis, research and definition of the structure of five new coordination compounds of Germanium(IV) and 3d-metals with 1-hydroxyethane-1,1-diphosphonic acid and 1,10-phenanthroline, which in crystals are organic-inorganic hybrid ensembles with three-dimensional networks formed by numerous intermolecular hydrogen bonds between complex cations, anions, and crystalline water molecules.