Abstract: | The crystal chemistry of the double salts Me+Cl · Me2+Cl2 · 2 H2O (where (Me+ = K, Rb, Cs; Me2+ = Mn, Fe, Co, Ni) is considered. It is concluded that these salts crystallize in three types of structures, the Me+ ion size being decisive for the structure type. Salts containing the large Cs+ ions crystallize in an orthorhombic structure in which Me2+ (H2O)2Cl4] octahedra form chains having common Cl? corners. Salts with the smaller K+ ions crystallize in a tricline system, the Me2+ (H2O)2Cl4] octahedra being connected by a common Cl–Cl edge and forming dimers. When the intermediate in size Rb+ ions are present in the salts, either of the above structures is possible as well as a monoclinic structure which is intermediate in symmetry. The expected isostructure of the cesium salts was checked by studing the CsCl · NiCl2 · 2 H2O–CsCl · MnCl2 · 2H2O–H2O system. A continuous series of mixed crystals is found. |