Crystal, electronic structure and hydrogenation properties of the Mg5.57Ni16Ge7.43 cluster phase with a new type of polyhedron

The ternary germanide Mg5.57Ni16Ge7.43 (cubic, space group Fmm, cF116) belongs to the structural family based on the Th6Mn23‐type. The Ge1 and Ge2 atoms fully occupy the 4a (mm symmetry) and 24d (m.mm) sites, respectively. The Ni1 and Ni2 atoms both fully occupy two 32f sites (.3m symmetry). The Mg/Ge statistical mixture occupies the 24e site with 4m.m symmetry. The structure of the title compound contains a three‐core‐shell cluster. At (0,0,0), there is a Ge1 atom which is surrounded by eight Ni atoms at the vertices of a cube and consequently six Mg atoms at the vertices of an octahedron. These surrounded eight Ni and six Mg atoms form a [Ge1Ni8(Mg/Ge)6] rhombic dodecahedron with a coordination number of 14. The [GeNi8(Mg/Ge)6] rhombic dodecahedron is encapsulated within the [Ni24] rhombicuboctahedron, which is again encapsulated within an [Ni32(Mg/Ge)24] pentacontatetrahedron; thus, the three‐core‐shell cluster [GeNi8(Mg/Ge)6@Ni24@Ni32(Mg/Ge)24] results. The pentacontatetrahedron is a new representative of Pavlyuk's polyhedra group based on pentagonal, tetragonal and trigonal faces. The dominance of the metallic type of bonding between atoms in the Mg5.57Ni16Ge7.43 structure is confirmed by the results of the electronic structure calculations. The hydrogen sorption capacity of this intermetallic at 570 K reaches 0.70 wt% H2. The crystal structure of the cubic ternary germanide Mg5.57Ni16Ge7.43 has been determined by single‐crystal X‐ray diffraction. The structure type represents the structure family based on the Th6Mn23‐type and Mg6Cu16Si7. A new type of polyhedron, i.e. a pentacontatetrahedron, which is based on triangular, tetragonal and pentagonal faces, is described. Electronic structure and hydrogenation properties are discussed.