Mixed crystals in the system Cu2MnGexSn1−xS4: Phase analytical investigations and inspection of tetrahedra volumes

Cu₂MnGeS₄ crystallizes orthorhombic in a wurtzite superstructure type while Cu₂MnSnS₄ crystallizes in a tetragonal sphalerite superstructure type. Lattice constants and thermal analyses of the solid solution series Cu₂MnGe_xSn_1−xS₄ are presented. A two-phase region is found from Cu₂MnGe_0.3Sn_0.7S₄ to Cu₂MnGe_0.5Sn_0.5S₄. The cell volume of the mixed crystals increases with increasing Sn content. The melting points increase smoothly with increasing Ge content to x=0.5 and then steeply for higher Ge contents. The single crystal X-ray structure analysis of Cu₂MnGe_0.55Sn_0.45S₄ is presented. The refinement converges to R=0.0270 and wR₂=0.0586, Z is 2. The volumes of the tetrahedra MS₄] (M=Cu, Mn, Ge, Sn) are calculated. From these volumes the differences in size of the tetrahedra are derived and compared with the corresponding differences in the end members of the solid solution series. It turns out that the resulting structure type in these materials depends on the volume differences of the constituting tetrahedra MS₄].