Li3BiO4 is Caswellsilverite-like structured and crystallizes in the cubic I-43m space group. Li(1) is bonded to one O(2) and five equivalent O(1) atoms to form distorted LiO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with three equivalent Bi(1)O6 octahedra, and edges with nine equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. 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)O6 octahedra, edges with three equivalent Bi(1)O6 octahedra, and edges with nine equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. There are two inequivalent O sites. In the first O site, O(1) is bonded to five equivalent Li(1) and one Bi(1) atom to form OLi5Bi octahedra that share corners with two equivalent O(2)Li3Bi3 octahedra, corners with four equivalent O(1)Li5Bi octahedra, edges with three equivalent O(2)Li3Bi3 octahedra, and edges with nine equivalent O(1)Li5Bi octahedra. The corner-sharing octahedral tilt angles range from 0-14°. In the second O site, O(2) is bonded to three equivalent Li(1) and three equivalent Bi(1) atoms to form OLi3Bi3 octahedra that share corners with six equivalent O(1)Li5Bi octahedra, edges with three equivalent O(2)Li3Bi3 octahedra, and edges with nine equivalent O(1)Li5Bi octahedra. The corner-sharing octahedral tilt angles range from 0-14°.
Li3BiO4 is Caswellsilverite-like structured and crystallizes in the cubic I-43m space group. Li(1) is bonded to one O(2) and five equivalent O(1) atoms to form distorted LiO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with three equivalent Bi(1)O6 octahedra, and edges with nine equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. The Li(1)-O(2) bond length is 2.53 Å. There are a spread of Li(1)-O(1) bond distances ranging from 2.01-2.30 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)O6 octahedra, edges with three equivalent Bi(1)O6 octahedra, and edges with nine equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. All Bi(1)-O(1) bond lengths are 2.05 Å. All Bi(1)-O(2) bond lengths are 2.28 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to five equivalent Li(1) and one Bi(1) atom to form OLi5Bi octahedra that share corners with two equivalent O(2)Li3Bi3 octahedra, corners with four equivalent O(1)Li5Bi octahedra, edges with three equivalent O(2)Li3Bi3 octahedra, and edges with nine equivalent O(1)Li5Bi octahedra. The corner-sharing octahedral tilt angles range from 0-14°. In the second O site, O(2) is bonded to three equivalent Li(1) and three equivalent Bi(1) atoms to form OLi3Bi3 octahedra that share corners with six equivalent O(1)Li5Bi octahedra, edges with three equivalent O(2)Li3Bi3 octahedra, and edges with nine equivalent O(1)Li5Bi octahedra. The corner-sharing octahedral tilt angles range from 0-14°.