The Phosphidosilicates AE2 Li4 SiP4 (AE=Ca, Sr, Eu) Ba4 Li16 Si3 P12

The quaternary phosphidosilicates AE2 Li4 SiP4 (AE=Ca, Sr, Eu) and Ba4 Li16 Si3 P12 were synthesized by heating the elements and Li3 P under argon atmosphere. Their crystal structures were determined by single crystal X-ray diffraction. AE2 Li4 SiP4 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. Ba4 Li16 Si3 P12 forms likewise a new structure type (P21 /c, Z=16) with a three-dimensional network of SiP4 , Si2 P6 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. 31 P and 29 Si solid-state NMR spectra confirm the crystal structures of the compounds AE2 Li4 SiP4 . 7 Li 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.