Li3BiO4 crystallizes in the monoclinic P2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-16°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Bi(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form BiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles are 16°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Bi(1) atom to form OLi5Bi octahedra that share corners with two equivalent O(1)Li5Bi octahedra, corners with four equivalent O(2)Li4Bi2 octahedra, edges with six equivalent O(2)Li4Bi2 octahedra, and edges with six equivalent O(1)Li5Bi octahedra. The corner-sharing octahedral tilt angles range from 5-18°. In the second O site, O(2) is bonded to one Li(1), one Li(3), two equivalent Li(2), and two equivalent Bi(1) atoms to form distorted OLi4Bi2 octahedra that share corners with two equivalent O(2)Li4Bi2 octahedra, corners with four equivalent O(1)Li5Bi octahedra, edges with six equivalent O(2)Li4Bi2 octahedra, and edges with six equivalent O(1)Li5Bi octahedra. The corner-sharing octahedral tilt angles range from 5-16°.
Li3BiO4 crystallizes in the monoclinic P2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. Both Li(1)-O(2) bond lengths are 2.28 Å. There are two shorter (2.12 Å) and two longer (2.19 Å) Li(1)-O(1) bond lengths. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-16°. Both Li(2)-O(1) bond lengths are 2.08 Å. There are two shorter (2.15 Å) and two longer (2.31 Å) Li(2)-O(2) bond lengths. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Both Li(3)-O(2) bond lengths are 2.57 Å. There are two shorter (2.01 Å) and two longer (2.09 Å) Li(3)-O(1) bond lengths. Bi(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form BiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles are 16°. Both Bi(1)-O(1) bond lengths are 2.06 Å. There are two shorter (2.14 Å) and two longer (2.17 Å) Bi(1)-O(2) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(3), and one Bi(1) atom to form OLi5Bi octahedra that share corners with two equivalent O(1)Li5Bi octahedra, corners with four equivalent O(2)Li4Bi2 octahedra, edges with six equivalent O(2)Li4Bi2 octahedra, and edges with six equivalent O(1)Li5Bi octahedra. The corner-sharing octahedral tilt angles range from 5-18°. In the second O site, O(2) is bonded to one Li(1), one Li(3), two equivalent Li(2), and two equivalent Bi(1) atoms to form distorted OLi4Bi2 octahedra that share corners with two equivalent O(2)Li4Bi2 octahedra, corners with four equivalent O(1)Li5Bi octahedra, edges with six equivalent O(2)Li4Bi2 octahedra, and edges with six equivalent O(1)Li5Bi octahedra. The corner-sharing octahedral tilt angles range from 5-16°.