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Li3PS 4 crystallizes in the orthorhombic system, space group Prima, with a = 13.066 (3), b = 8.015 (2), c = 6.101 (2)A, V=639/ka, z=4, dm = 1.85, dx= 1.87Mg m -3. With Mo Kt~ radiation (2 = 0.71069 ,~,/t = 1.5 mm-~), the structure was refined to R = 0.046 with 255 independent reflexions (0 < 30 °). Tetrahedral PSIanions (mean P-S length 2.050 ]~) are centered on mirror planes; three kinds of Li + ions are revealed in the asymmetric unit: Li(1) in a fully filled site (tetrahedral coordination: Li...S ~_ 2.46/~); and Li(2) and Li(3) with occupancy factors of 0.7 and 0.3 0567-7408/82/071887-04501.00 respectively, so that diffusion of Li + through Li(2)-Li(3)--Li(2) tunnels with a 2.52]k jump between vicinal sites could be expected.

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