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The stannides Li 8 Rh 7 Sn 8  and Li 1.23 Rh 1.77 Sn were synthesized from the elements in sealed niobium ampoules. The structures were refined on the basis of single crystal X-ray diffractometer data: MnCu 2 Al type (Heusler phase),  Fm -3 m ,  a  = 615.5(4) pm,  wR 2 = 0.0319, 106 F  2  values, 6 variables for Li 1.23 Rh 1.77 Sn and  P -3 m 1,  a  = 894.4(4) pm,  c  = 1107.3(4) pm,  wR 2 = 0.0600, 1287 F  2  values, 48 variables for Li 8 Rh 7 Sn 8  which crystallizes with a new structure type. The rhodium site in Li 1.23 Rh 1.77 Sn shows Rh/Li mixing. The structure of Li 8 Rh 7 Sn 8  contains two pronounced structural motifs. Layers of edge-sharing RhSn 6  octahedra alternate with layers of six-membered rings of corner-sharing SnRh 4  tetrahedra in UDUDUD orientation. The [Rh 7 Sn 8 ]  δ –  polyanionic network is characterized by covalent rhodium-tin bonding.

Synthesis and structure of Li 8 Rh 7 Sn 8 and Li 1.23 Rh 1.77 Sn