The Phosphidosilicates AE2Li4SiP4 (AE=Ca, Sr, Eu) Ba4Li16Si3P12

The quaternary phosphidosilicates AE2Li4SiP4 (AE=Ca, Sr, Eu) and Ba4Li16Si3P12 were synthesized by heating the elements and Li3P under argon atmosphere. Their crystal structures were determined by single crystal X‐ray diffraction. AE2Li4SiP4 crystallize in a new layered structure type (P21/m, Z=2) with CdI2‐analoguos layers. Edge sharing CaP6 octahedra are separated by layers of vertex‐sharing SiP4 and LiP4 tetrahedra, which contain additional chains of LiP6 octahedra. Ba4Li16Si3P12 forms likewise a new structure type (P21/c, Z=16) with a three‐dimensional network of SiP4, Si2P6 and LiP4 entities as well as one phosphorus site not bonded to silicon. Barium is located in capped trigonal prisms of phosphorus which form strongly corrugated layers. 31P and 29Si solid‐state NMR spectra confirm the crystal structures of the compounds AE2Li4SiP4. 7Li spectra show only one signal in spite of quite different crystallographic positions, which indicate possible Li+ mobility. However, this signal is much broader compared to the known Li+ conducting phosphidosilicates. Accordingly, electrochemical impedance measurements show low Li+ conductivities. The new quaternary phosphidosilicates AE2Li4SiP4 (AE=Ca, Sr, Eu) and Ba4Li16Si3P12 contain so far unknown structural motifs with lithium in octahedral and tetrahedral coordination by phosphorus