Dedicated to Prof. Wolfgang Schnick on the occasion of his 65 th birthday. Li 3 AlAs 2 , Li 3 GaAs 2 and Li 3 InAs 2 were obtained from the elements via high temperature synthesis. Li 3 AlAs 2 and Li 3 GaAs 2 crystallize in a distorted 2 • 2 • 1 superstructure of the antifluorite structure type. The orthorhombic crystal structure is isotypic to Li 3 AlP 2 and Li 3 GaP 2 , space group Cmce (No. 64) showing layers of condensed TrAs 4 -tetrahedra (Tr = Al, Ga). Li 3 InAs 2 crystallizes isotypic to Li 3 InP 2 in a distorted 2 • 2 • 4 antifluorite type super-structure. The crystal structure is tetragonal, space group I4 1 / acd (No. 142), showing a 3D-network of In 4 As 10 -supertetrahedra. Structural characterization by powder X-ray diffraction, thermal analysis, conductivity measurements and band structure calculations show ion conductivity for Li 3 InAs 2 and electronic charge transport for Li 3 AlAs 2 and Li 3 GaAs 2 .
Dedicated to Prof. Josef Breu on the occasion of his 60 th birthday.Phase pure Li 3 As and Li 3 P were synthesized from the elements by a high temperature route. Crystal structures were refined from powder X-ray diffraction data. The title compounds were further characterized by difference thermal analysis, temperature dependent X-ray powder diffraction and impedance spectroscopy, proving unexpected Li ion conductivity for Li 3 As. High pressure behaviour of the title compounds was modeled via density functional theory, confirming the experimentally reported cubic modifications of Li 3 P and Li 3 As.
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