The study describes synthesis methods, structural features and thermal stability of the novel cation‐anionic coordination compounds, crystallized in Sohnke chiral space group P21 [Zn(phen)3]2[Ge2(OH)(HTart)(μ‐Tart)2] ⋅ 23H2O (1) and [Zn(bipy)3][Ge2(OH)2(μ‐Tart)2] ⋅ 5H2O (2). Dependently on the second heterocyclic ligand (1,10‐phenanthroline ‐ phen (1) or 2,2’‐bipyridine ‐bipy (2)) complex zinc cations showed their ability to recognize selectively two different types of anions: dimeric [Ge2(OH)2(μ‐Tart)2]2− (2) and more complex [Ge2(OH)(HTart)(μ‐Tart)2]4− (1) with additional terminal tartaric acid ligand (HTart3−) and different coordination polyhedrons of Ge in its structure. Compounds 1 and 2 were characterized by X‐Ray, IR, MS and thermogravimetric analyzes. Analysis of intermolecular interactions using Hirshfeld surface‐based tools indicated the dominant role of various hydrogen intermolecular interactions such as H…H, H…O for both compounds, and C…C (π⋅⋅⋅π) for 1.