Li8HfO6 crystallizes in the hexagonal P6_3cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Hf(1)O4 tetrahedra, corners with six equivalent Li(1)O4 tetrahedra, and edges with two equivalent Li(3)O4 tetrahedra. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(3), and two equivalent O(2) atoms. In the third Li site, Li(3) is bonded to one O(2) and three equivalent O(1) atoms to form LiO4 tetrahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Hf(1)O4 tetrahedra, and edges with three equivalent Li(1)O4 tetrahedra. Hf(1) is bonded to one O(3) and three equivalent O(1) atoms to form HfO4 tetrahedra that share corners with six equivalent Li(1)O4 tetrahedra and corners with six equivalent Li(3)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and one Hf(1) atom to form corner-sharing OLi4Hf trigonal bipyramids. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Li(3), three equivalent Li(1), and three equivalent Li(2) atoms. In the third O site, O(3) is bonded in a 7-coordinate geometry to three equivalent Li(1), three equivalent Li(2), and one Hf(1) atom.
Li8HfO6 crystallizes in the hexagonal P6_3cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Hf(1)O4 tetrahedra, corners with six equivalent Li(1)O4 tetrahedra, and edges with two equivalent Li(3)O4 tetrahedra. The Li(1)-O(1) bond length is 1.96 Å. The Li(1)-O(3) bond length is 2.10 Å. Both Li(1)-O(2) bond lengths are 2.03 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(3), and two equivalent O(2) atoms. The Li(2)-O(1) bond length is 2.00 Å. The Li(2)-O(3) bond length is 2.40 Å. Both Li(2)-O(2) bond lengths are 1.97 Å. In the third Li site, Li(3) is bonded to one O(2) and three equivalent O(1) atoms to form LiO4 tetrahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Hf(1)O4 tetrahedra, and edges with three equivalent Li(1)O4 tetrahedra. The Li(3)-O(2) bond length is 2.12 Å. All Li(3)-O(1) bond lengths are 1.97 Å. Hf(1) is bonded to one O(3) and three equivalent O(1) atoms to form HfO4 tetrahedra that share corners with six equivalent Li(1)O4 tetrahedra and corners with six equivalent Li(3)O4 tetrahedra. The Hf(1)-O(3) bond length is 1.98 Å. All Hf(1)-O(1) bond lengths are 1.95 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and one Hf(1) atom to form corner-sharing OLi4Hf trigonal bipyramids. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Li(3), three equivalent Li(1), and three equivalent Li(2) atoms. In the third O site, O(3) is bonded in a 7-coordinate geometry to three equivalent Li(1), three equivalent Li(2), and one Hf(1) atom.