Li(BiO2)2 crystallizes in the orthorhombic Pbca space group. 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(1)O6 octahedra, corners with four equivalent Bi(1)O6 octahedra, edges with four equivalent Bi(1)O6 octahedra, and faces with two equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-55°. Bi(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form distorted BiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with ten equivalent Bi(1)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 33-70°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Li(1) and three equivalent Bi(1) atoms. In the second O site, O(2) is bonded to one Li(1) and three equivalent Bi(1) atoms to form distorted corner-sharing OLiBi3 tetrahedra.
Li(BiO2)2 crystallizes in the orthorhombic Pbca space group. 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(1)O6 octahedra, corners with four equivalent Bi(1)O6 octahedra, edges with four equivalent Bi(1)O6 octahedra, and faces with two equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-55°. Both Li(1)-O(2) bond lengths are 2.38 Å. There are two shorter (2.12 Å) and two longer (2.25 Å) Li(1)-O(1) bond lengths. Bi(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form distorted BiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with ten equivalent Bi(1)O6 octahedra,  an edgeedge with one Bi(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 33-70°. There are a spread of Bi(1)-O(1) bond distances ranging from 2.27-2.52 Å. There are a spread of Bi(1)-O(2) bond distances ranging from 2.23-2.37 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Li(1) and three equivalent Bi(1) atoms. In the second O site, O(2) is bonded to one Li(1) and three equivalent Bi(1) atoms to form distorted corner-sharing OLiBi3 tetrahedra.