Mo₄FeGa_17.25- x Ge _x : Complementary Point Substitutions, Buffering Frameworks, and Merging of the 18‑n and Octet...

We present the discovery of Mo₄FeGa_17.25-x Ge _x (x ∼ 2.1(4), based on determination of Ge content), a complex gallide featuring a variety of point substitution phenomena. Its crystal structure is derived from the Ti₂Ni type, in which a diamond network of face-sharing octahedra is interpenetrated by a second diamond network of vertex-sharing stella quadrangula. However, while in the ideal Ti₂Ni type these two frameworks run uninterrupted through the crystal, Mo₄FeGa_17.25-x Ge _x shows three variations. First, the inner tetrahedron of every other stella quadrangula is replaced with a main group atom, creating tetrahedra reminiscent of the Zintl phase NaTl. Next, a selection of Ga₆ octahedra are filled with Fe atoms, in a manner analogous to the stuffed AuCu₃-type phases. Finally, the refined crystal structure shows that in each unit cell a single Ga2 atom in the octahedral network is substituted with a dumbbell of Ga/Ge atoms. Electronic structure calculations on ordered models of Mo₄FeGa_17.25-x Ge _x reveal a narrow band near the Fermi energy, which is explained in terms of the 18-n and octet bonding schemes using reversed approximation Molecular Orbital analysis. A DFT-chemical pressure analysis connects the tetrahedron/atom and atom/dumbbell substitutions to the relief of atomic packing tensions and highlights soft atomic motions within the octahedral framework and driving forces for atom/dumbbell substitution. The combination of soft vibrational modes, disorder, and a narrow band gap could make this phase of interest for potential thermoelectric properties.