Li8PSe6 crystallizes in the tetragonal I-4 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one Se(2), one Se(3), and two equivalent Se(1) atoms. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one Se(2), one Se(3), and two equivalent Se(1) atoms. P(1) is bonded in a tetrahedral geometry to four equivalent Se(1) atoms. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one P(1) atom. In the second Se site, Se(2) is bonded in a 8-coordinate geometry to four equivalent Li(1) and four equivalent Li(2) atoms. In the third Se site, Se(3) is bonded in a 8-coordinate geometry to four equivalent Li(1) and four equivalent Li(2) atoms.
Li8PSe6 crystallizes in the tetragonal I-4 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one Se(2), one Se(3), and two equivalent Se(1) atoms. The Li(1)-Se(2) bond length is 2.46 Å. The Li(1)-Se(3) bond length is 2.85 Å. There is one shorter (2.51 Å) and one longer (2.71 Å) Li(1)-Se(1) bond length. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one Se(2), one Se(3), and two equivalent Se(1) atoms. The Li(2)-Se(2) bond length is 2.98 Å. The Li(2)-Se(3) bond length is 2.63 Å. There is one shorter (2.50 Å) and one longer (2.66 Å) Li(2)-Se(1) bond length. P(1) is bonded in a tetrahedral geometry to four equivalent Se(1) atoms. All P(1)-Se(1) bond lengths are 2.36 Å. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one P(1) atom. In the second Se site, Se(2) is bonded in a 8-coordinate geometry to four equivalent Li(1) and four equivalent Li(2) atoms. In the third Se site, Se(3) is bonded in a 8-coordinate geometry to four equivalent Li(1) and four equivalent Li(2) atoms.