Li7BiO6 crystallizes in the triclinic P1 space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(7)O4 tetrahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Li(5)O4 tetrahedra, and  an edgeedge with one Li(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 9-62°. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with three equivalent Li(7)O4 tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Li(5)O4 tetrahedra, and  an edgeedge with one Li(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-56°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra, corners with two equivalent Li(7)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Bi(1)O6 octahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra,  an edgeedge with one Li(6)O4 tetrahedra,  an edgeedge with one Li(7)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(6) atom. In the fifth Li site, Li(5) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with three equivalent Li(6)O4 tetrahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(7)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 12-56°. In the sixth Li site, Li(6) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with three equivalent Li(5)O4 tetrahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(7)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 21-54°. In the seventh Li site, Li(7) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Li(5)O4 tetrahedra, and  an edgeedge with one Li(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 14-62°. Bi(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form BiO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra, corners with two equivalent Li(7)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra,  an edgeedge with one Li(6)O4 tetrahedra,  an edgeedge with one Li(7)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(7), and one Bi(1) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), one Li(4), one Li(5), one Li(6), and one Bi(1) atom. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Bi(1) atom to form a mixture of distorted corner and edge-sharing OLi5Bi pentagonal pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(7), and one Bi(1) atom to form a mixture of distorted corner and edge-sharing OLi6Bi pentagonal bipyramids. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(6), one Li(7), and one Bi(1) atom. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to one Li(3), one Li(4), one Li(5), one Li(6), one Li(7), and one Bi(1) atom.
Li7BiO6 crystallizes in the triclinic P1 space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(7)O4 tetrahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Li(5)O4 tetrahedra, and  an edgeedge with one Li(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 9-62°. The Li(1)-O(1) bond length is 1.84 Å. The Li(1)-O(2) bond length is 1.94 Å. The Li(1)-O(4) bond length is 2.11 Å. The Li(1)-O(5) bond length is 2.06 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with three equivalent Li(7)O4 tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Li(5)O4 tetrahedra, and  an edgeedge with one Li(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-56°. The Li(2)-O(1) bond length is 1.90 Å. The Li(2)-O(3) bond length is 1.94 Å. The Li(2)-O(4) bond length is 2.13 Å. The Li(2)-O(5) bond length is 1.93 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra, corners with two equivalent Li(7)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Bi(1)O6 octahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra,  an edgeedge with one Li(6)O4 tetrahedra,  an edgeedge with one Li(7)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The Li(3)-O(1) bond length is 2.13 Å. The Li(3)-O(2) bond length is 2.32 Å. The Li(3)-O(3) bond length is 2.20 Å. The Li(3)-O(4) bond length is 2.15 Å. The Li(3)-O(5) bond length is 2.25 Å. The Li(3)-O(6) bond length is 2.51 Å. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one O(6) atom. The Li(4)-O(1) bond length is 2.50 Å. The Li(4)-O(2) bond length is 2.07 Å. The Li(4)-O(3) bond length is 2.01 Å. The Li(4)-O(4) bond length is 2.28 Å. The Li(4)-O(6) bond length is 2.07 Å. In the fifth Li site, Li(5) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with three equivalent Li(6)O4 tetrahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(7)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 12-56°. The Li(5)-O(2) bond length is 1.82 Å. The Li(5)-O(3) bond length is 1.91 Å. The Li(5)-O(4) bond length is 1.97 Å. The Li(5)-O(6) bond length is 1.94 Å. In the sixth Li site, Li(6) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with three equivalent Li(5)O4 tetrahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(7)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 21-54°. The Li(6)-O(2) bond length is 1.92 Å. The Li(6)-O(3) bond length is 2.01 Å. The Li(6)-O(5) bond length is 1.94 Å. The Li(6)-O(6) bond length is 1.85 Å. In the seventh Li site, Li(7) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra,  an edgeedge with one Li(5)O4 tetrahedra, and  an edgeedge with one Li(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 14-62°. The Li(7)-O(1) bond length is 1.90 Å. The Li(7)-O(4) bond length is 1.98 Å. The Li(7)-O(5) bond length is 2.02 Å. The Li(7)-O(6) bond length is 1.95 Å. Bi(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form BiO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent Li(6)O4 tetrahedra, corners with two equivalent Li(7)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(2)O4 tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra,  an edgeedge with one Li(6)O4 tetrahedra,  an edgeedge with one Li(7)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The Bi(1)-O(1) bond length is 2.12 Å. The Bi(1)-O(2) bond length is 2.11 Å. The Bi(1)-O(3) bond length is 2.13 Å. The Bi(1)-O(4) bond length is 2.14 Å. The Bi(1)-O(5) bond length is 2.14 Å. The Bi(1)-O(6) bond length is 2.10 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(7), and one Bi(1) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), one Li(4), one Li(5), one Li(6), and one Bi(1) atom. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Bi(1) atom to form a mixture of distorted corner and edge-sharing OLi5Bi pentagonal pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(7), and one Bi(1) atom to form a mixture of distorted corner and edge-sharing OLi6Bi pentagonal bipyramids. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(6), one Li(7), and one Bi(1) atom. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to one Li(3), one Li(4), one Li(5), one Li(6), one Li(7), and one Bi(1) atom.