Li10GeP2S12 crystallizes in the tetragonal P4_2mc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one S(1), one S(4), one S(5), and one S(6) atom. In the second Li site, Li(2) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(5) atoms to form LiS6 octahedra that share corners with two equivalent P(2)S4 tetrahedra and edges with two equivalent P(1)S4 tetrahedra. In the third Li site, Li(3) is bonded to two equivalent S(2), two equivalent S(4), and two equivalent S(6) atoms to form distorted LiS6 octahedra that share corners with two equivalent P(2)S4 tetrahedra and edges with two equivalent Ge(1)S4 tetrahedra. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one S(1), one S(2), one S(3), one S(4), and one S(6) atom. Ge(1) is bonded to two equivalent S(4) and two equivalent S(6) atoms to form GeS4 tetrahedra that share edges with two equivalent Li(3)S6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent S(3) and two equivalent S(5) atoms to form PS4 tetrahedra that share edges with two equivalent Li(2)S6 octahedra. In the second P site, P(2) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form PS4 tetrahedra that share corners with two equivalent Li(2)S6 octahedra and corners with two equivalent Li(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 42-48°. There are six inequivalent S sites. In the first S site, S(3) is bonded to one Li(2), two equivalent Li(4), and one P(1) atom to form a mixture of edge and corner-sharing SLi3P trigonal pyramids. In the second S site, S(4) is bonded in a distorted hexagonal planar geometry to one Li(3), two equivalent Li(1), two equivalent Li(4), and one Ge(1) atom. In the third S site, S(5) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one P(1) atom. In the fourth S site, S(6) is bonded in a 6-coordinate geometry to one Li(3), two equivalent Li(1), two equivalent Li(4), and one Ge(1) atom. In the fifth S site, S(1) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), two equivalent Li(4), and one P(2) atom. In the sixth S site, S(2) is bonded to one Li(3), two equivalent Li(4), and one P(2) atom to form distorted corner-sharing SLi3P trigonal pyramids.
Li10GeP2S12 crystallizes in the tetragonal P4_2mc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one S(1), one S(4), one S(5), and one S(6) atom. The Li(1)-S(1) bond length is 2.52 Å. The Li(1)-S(4) bond length is 2.76 Å. The Li(1)-S(5) bond length is 2.43 Å. The Li(1)-S(6) bond length is 2.41 Å. In the second Li site, Li(2) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(5) atoms to form LiS6 octahedra that share corners with two equivalent P(2)S4 tetrahedra and edges with two equivalent P(1)S4 tetrahedra. Both Li(2)-S(1) bond lengths are 2.71 Å. Both Li(2)-S(3) bond lengths are 2.60 Å. Both Li(2)-S(5) bond lengths are 2.66 Å. In the third Li site, Li(3) is bonded to two equivalent S(2), two equivalent S(4), and two equivalent S(6) atoms to form distorted LiS6 octahedra that share corners with two equivalent P(2)S4 tetrahedra and edges with two equivalent Ge(1)S4 tetrahedra. Both Li(3)-S(2) bond lengths are 2.80 Å. Both Li(3)-S(4) bond lengths are 2.60 Å. Both Li(3)-S(6) bond lengths are 2.63 Å. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one S(1), one S(2), one S(3), one S(4), and one S(6) atom. The Li(4)-S(1) bond length is 2.92 Å. The Li(4)-S(2) bond length is 2.39 Å. The Li(4)-S(3) bond length is 2.47 Å. The Li(4)-S(4) bond length is 2.62 Å. The Li(4)-S(6) bond length is 2.86 Å. Ge(1) is bonded to two equivalent S(4) and two equivalent S(6) atoms to form GeS4 tetrahedra that share edges with two equivalent Li(3)S6 octahedra. Both Ge(1)-S(4) bond lengths are 2.25 Å. Both Ge(1)-S(6) bond lengths are 2.24 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent S(3) and two equivalent S(5) atoms to form PS4 tetrahedra that share edges with two equivalent Li(2)S6 octahedra. Both P(1)-S(3) bond lengths are 2.07 Å. Both P(1)-S(5) bond lengths are 2.04 Å. In the second P site, P(2) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form PS4 tetrahedra that share corners with two equivalent Li(2)S6 octahedra and corners with two equivalent Li(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 42-48°. Both P(2)-S(1) bond lengths are 2.07 Å. Both P(2)-S(2) bond lengths are 2.04 Å. There are six inequivalent S sites. In the first S site, S(3) is bonded to one Li(2), two equivalent Li(4), and one P(1) atom to form a mixture of edge and corner-sharing SLi3P trigonal pyramids. In the second S site, S(4) is bonded in a distorted hexagonal planar geometry to one Li(3), two equivalent Li(1), two equivalent Li(4), and one Ge(1) atom. In the third S site, S(5) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Li(1), and one P(1) atom. In the fourth S site, S(6) is bonded in a 6-coordinate geometry to one Li(3), two equivalent Li(1), two equivalent Li(4), and one Ge(1) atom. In the fifth S site, S(1) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), two equivalent Li(4), and one P(2) atom. In the sixth S site, S(2) is bonded to one Li(3), two equivalent Li(4), and one P(2) atom to form distorted corner-sharing SLi3P trigonal pyramids.