Twisted Kelvin Cells and Truncated Octahedral Cages in the Crystal Structures of Unconventional Clathrates, AM2P4 (A = Sr, Ba; M = Cu, Ni)

A new strontium nickel polyphosphide, SrNi2P4, was synthesized from elements and structurally characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic space group Fddd (No. 70), with Z = 8. The crystal structure is that of a clathrate type, composed of Ni8P16, 14-faced polyhedral cages that encapsulate Sr atoms. Together with the previously reported but unrecognized clathrate VII, BaNi2P4, and another previously reported clathrate, BaCu2P4, which is isostructural to SrNi2P4, a family of transition metal–phosphorus clathrates is represented. The crystal structures of each of the discussed transition metal-based clathrates are composed of unique polyhedra containing square faces. These structural fragments were predicted to be unstable for the conventional clathrates based on Si, Ge, and Sn. In this work, we report the crystal and electronic structures, chemical bonding, as well as the thermoelectric properties of this novel class of unconventional clathrates.