Mixed-metal phosphates K1.64Na0.36TiFe(PO4)3 and K0.97Na1.03Ti1.26Fe0.74(PO4)3 with a langbeinite framework

Single crystals of the langbeinite-type phosphates K1.65Na0.35TiFe(PO4)3 and K0.97Na1.03Ti1.26Fe0.74(PO4)3 were grown by crystallization from high-temperature self-fluxes in the system Na2O–K2O–P2O5–TiO2–Fe2O3 using fixed molar ratios of (Na+K):P = 1.0, Ti:P = 0.20 and Na:K = 1.0 or 2.0 over the temperature range 1273–953 K. The three-dimensional framework of the two isotypic phosphates are built up from [(Ti/Fe)2(PO4)3] structure units containing two mixed [(Ti/Fe)O6] octa­hedra (site symmetry 3) connected via three bridging PO4 tetra­hedra. The potassium and sodium cations share two different sites in the structure that are located in the cavities of the framework. One of these sites has nine and the other twelve surrounding O atoms.