Li2BiO3 crystallizes in the orthorhombic Cmmm space group. Li(1) is bonded to two equivalent O(2) and three equivalent O(1) atoms to form LiO5 trigonal bipyramids that share corners with two equivalent Bi(1)O6 octahedra, corners with six equivalent Li(1)O5 trigonal bipyramids, edges with four equivalent Bi(1)O6 octahedra, and edges with three equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 50°. Bi(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form BiO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with four equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Bi(1)O6 octahedra, and edges with eight equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedra are not tilted. There are two inequivalent O sites. In the first O site, O(2) is bonded to four equivalent Li(1) and two equivalent Bi(1) atoms to form OLi4Bi2 octahedra that share corners with two equivalent O(2)Li4Bi2 octahedra, corners with four equivalent O(1)Li3Bi2 trigonal bipyramids, edges with two equivalent O(2)Li4Bi2 octahedra, and edges with eight equivalent O(1)Li3Bi2 trigonal bipyramids. The corner-sharing octahedra are not tilted. In the second O site, O(1) is bonded to three equivalent Li(1) and two equivalent Bi(1) atoms to form OLi3Bi2 trigonal bipyramids that share corners with two equivalent O(2)Li4Bi2 octahedra, corners with six equivalent O(1)Li3Bi2 trigonal bipyramids, edges with four equivalent O(2)Li4Bi2 octahedra, and edges with three equivalent O(1)Li3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 48°.
Li2BiO3 crystallizes in the orthorhombic Cmmm space group. Li(1) is bonded to two equivalent O(2) and three equivalent O(1) atoms to form LiO5 trigonal bipyramids that share corners with two equivalent Bi(1)O6 octahedra, corners with six equivalent Li(1)O5 trigonal bipyramids, edges with four equivalent Bi(1)O6 octahedra, and edges with three equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 50°. Both Li(1)-O(2) bond lengths are 2.29 Å. There is one shorter (1.91 Å) and two longer (2.20 Å) Li(1)-O(1) bond lengths. Bi(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form BiO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with four equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Bi(1)O6 octahedra, and edges with eight equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedra are not tilted. Both Bi(1)-O(2) bond lengths are 2.19 Å. All Bi(1)-O(1) bond lengths are 2.24 Å. There are two inequivalent O sites. In the first O site, O(2) is bonded to four equivalent Li(1) and two equivalent Bi(1) atoms to form OLi4Bi2 octahedra that share corners with two equivalent O(2)Li4Bi2 octahedra, corners with four equivalent O(1)Li3Bi2 trigonal bipyramids, edges with two equivalent O(2)Li4Bi2 octahedra, and edges with eight equivalent O(1)Li3Bi2 trigonal bipyramids. The corner-sharing octahedra are not tilted. In the second O site, O(1) is bonded to three equivalent Li(1) and two equivalent Bi(1) atoms to form OLi3Bi2 trigonal bipyramids that share corners with two equivalent O(2)Li4Bi2 octahedra, corners with six equivalent O(1)Li3Bi2 trigonal bipyramids, edges with four equivalent O(2)Li4Bi2 octahedra, and edges with three equivalent O(1)Li3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 48°.