Li2BBiO5 crystallizes in the tetragonal P4/nmm 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 two equivalent Li(1)O6 octahedra, corners with four equivalent B(1)O4 tetrahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 29°. B(1) is bonded to four equivalent O(1) atoms to form BO4 tetrahedra that share corners with eight equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. Bi(1) is bonded in a 5-coordinate geometry to one O(2) and four equivalent O(1) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one B(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to four equivalent Li(1) and one Bi(1) atom.
Li2BBiO5 crystallizes in the tetragonal P4/nmm 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 two equivalent Li(1)O6 octahedra, corners with four equivalent B(1)O4 tetrahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 29°. Both Li(1)-O(2) bond lengths are 2.30 Å. All Li(1)-O(1) bond lengths are 2.16 Å. B(1) is bonded to four equivalent O(1) atoms to form BO4 tetrahedra that share corners with eight equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. All B(1)-O(1) bond lengths are 1.49 Å. Bi(1) is bonded in a 5-coordinate geometry to one O(2) and four equivalent O(1) atoms. The Bi(1)-O(2) bond length is 2.04 Å. All Bi(1)-O(1) bond lengths are 2.14 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one B(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to four equivalent Li(1) and one Bi(1) atom.