Li7BiO6 is Ilmenite-like structured and crystallizes in the trigonal R3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with six equivalent Li(1)O4 tetrahedra,  an edgeedge with one Bi(1)O6 octahedra, and edges with three equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 24-52°. In the second Li site, Li(2) is bonded to one O(2) and three equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with six equivalent Li(2)O4 tetrahedra,  an edgeedge with one Bi(1)O6 octahedra, and edges with three equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-55°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(2) atoms. Bi(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form BiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent Li(2)O4 tetrahedra, edges with three equivalent Li(1)O4 tetrahedra, and edges with three equivalent Li(2)O4 tetrahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), three equivalent Li(2), and one Bi(1) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), three equivalent Li(1), and one Bi(1) atom.
Li7BiO6 is Ilmenite-like structured and crystallizes in the trigonal R3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with six equivalent Li(1)O4 tetrahedra,  an edgeedge with one Bi(1)O6 octahedra, and edges with three equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 24-52°. The Li(1)-O(1) bond length is 2.00 Å. There are a spread of Li(1)-O(2) bond distances ranging from 1.84-2.03 Å. In the second Li site, Li(2) is bonded to one O(2) and three equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with six equivalent Li(2)O4 tetrahedra,  an edgeedge with one Bi(1)O6 octahedra, and edges with three equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-55°. The Li(2)-O(2) bond length is 1.95 Å. There is one shorter (1.94 Å) and two longer (1.99 Å) Li(2)-O(1) bond lengths. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(2) atoms. All Li(3)-O(1) bond lengths are 2.06 Å. All Li(3)-O(2) bond lengths are 2.48 Å. Bi(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form BiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent Li(2)O4 tetrahedra, edges with three equivalent Li(1)O4 tetrahedra, and edges with three equivalent Li(2)O4 tetrahedra. All Bi(1)-O(1) bond lengths are 2.15 Å. All Bi(1)-O(2) bond lengths are 2.11 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), three equivalent Li(2), and one Bi(1) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), three equivalent Li(1), and one Bi(1) atom.