Li6PO5Br and Li6PO5Cl: The first Lithium-Oxide-Argyrodites

The title compounds Li6PO5Br (F (4) over bar 3m, a = 8.297(1) angstrom, Z = 4) and Li6PO5Cl (F (4) over bar 3m, a = 8.2234(9) angstrom, Z = 4) represent the first oxidic argyrodites in general and the first lithiumoxoargyrodites in particular. The overall crystal structure corresponds to the cubic high temperature (HT) modification of all known cubic argyrodites, however, with a seemingly small but important difference concerning the lithium positions. In all other HT argyrodites with similar lithium content the 24 lithium atoms per unit cell are disordered over a 48 fold position in close vicinity to a 24 fold one causing a high mobility of the Li+. In the title compounds, however, they occupy the 24 fold one in a strictly ordered manner thus establishing a planar triangular first sphere coor-dination environment. This detail is of great importance for the amount of the specific lithium ionic conductivity and for the possible phase transition to an LT (low temperature) modification accompanied by an ordering of the disordered lithium atoms. Apparently the latter transition is suppressed in the title compounds because the Li+ are already frozen out in the cubic (HT = LT) form. The initially open question how this structural peculiarity influences the ionic conductivity (strengthening or weakening in comparison to oxygen free argyrodites?) is answered by a series of impedance measurements. The specific lithium ionic conductivity of the title compounds in the range 313 K < T < 518 K is significantly lower than in oxygen free argyrodites.