Polar-Covalent Bonding Beyond the Zintl Picture in Intermetallic Rare-Earth Germanides.

A comparative chemical bonding analysis for the germanides La2 MGe6 (M=Li, Mg, Al, Zn, Cu, Ag, Pd) and Y2 PdGe6 is presented, together with the crystal structure determination for M=Li, Mg, Cu, Ag. The studied compounds adopt the two closely related structure types oS72-Ce2 (Ga0.1 Ge0.9 )7 and mS36-La2 AlGe6 , containing zigzag chains and corrugated layers of Ge atoms bridged by M species, with La/Y atoms located in the biggest cavities. Chemical bonding was studied by means of the quantum chemical position-space techniques QTAIM (quantum theory of atoms in molecules), ELI-D (electron localizability indicator), and their basin intersections. The new penultimate shell correction (PSC0) method was introduced to adapt the ELI-D valence electron count to that expected from the periodic table of the elements. It plays a decisive role to balance the Ge-La polar-covalent interactions against the Ge-M ones. In spite of covalently bonded Ge partial structures formally obeying the Zintl electron count for M=Mg2+ , Zn2+ , all the compounds reveal noticeable deviations from the conceptual 8-N picture due to significant polar-covalent interactions of Ge with La and M ≠ Li, Mg atoms. For M=Li, Mg a formulation as a germanolanthanate M[La2 Ge6 ] is appropriate. Moreover, the relative Laplacian of ELI-D was discovered to reveal a chemically useful fine structure of the ELI-D distribution being related to polyatomic bonding features. With the aid of this new tool, a consistent picture of La/Y-M interactions for the title compounds was extracted.