Icosahedral Li clusters in the structures of Li33.3Ba13.1Ca3 and Li18.9Na8.3Ba15.3

The intermetallic phases Li33.3Ba13.1Ca3 and Li18.9Na8.3Ba15.3 have been prepared and their crystal structures have been determined. According to single-crystal X-ray diffraction data, both compounds crystallize in new structure types with trigonal unit cells (Li33.3Ba13.1Ca3: R3¯c, a=19.9127(4) Å, c=90.213(3) Å, Z=18, V=30,978(1) Å3 and Li18.9Na8.3Ba15.3: P3¯, a=20.420(3) Å, c=92.914(19), Z=18, V=33,550(10) Å3). The first compound can be described as a complicated variant of the arsenic structure. The second has similar packing of the Ba atoms but differs from the Ca-containing phase in the packing of the light elements. Both compounds contain icosahedron-based polytetrahedral clusters, typical for Li-rich phases, e.g. Ba19Li44.