Abstract (PDF) Graphical Abstract: Two crystalline compounds of germanium(IV) with malic acid (HMal) and 1,10ʹ-phenanthroline (phen) - [Ge(HMal)2(phen)]•pheh•2H2O (I) and [CuCl(phen)2][Ge(OH)(HMal)2] (II) were synthesized for the first time and characterized by elemental analysis, IR-spectroscopy and thermogravimetric analysis. There was elucidated from single-crystal X-ray diffraction that two different forms of Germanium are implemented: Ge4+ (I) and hydrolyzed GeOH3+ (II) to form distorted octahedron and pyramid respectively.