Li2BBiO4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent B(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. B(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form BO4 tetrahedra that share corners with eight equivalent Li(1)O4 tetrahedra. Bi(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(1), and two equivalent O(3) atoms. There are three 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 distorted trigonal pyramidal geometry to two equivalent Li(1), one B(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Li(1), one B(1), and two equivalent Bi(1) atoms.
Li2BBiO4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent B(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The Li(1)-O(2) bond length is 1.97 Å. The Li(1)-O(3) bond length is 2.07 Å. There is one shorter (1.95 Å) and one longer (1.98 Å) Li(1)-O(1) bond length. B(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form BO4 tetrahedra that share corners with eight equivalent Li(1)O4 tetrahedra. The B(1)-O(2) bond length is 1.53 Å. The B(1)-O(3) bond length is 1.55 Å. Both B(1)-O(1) bond lengths are 1.47 Å. Bi(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(1), and two equivalent O(3) atoms. The Bi(1)-O(2) bond length is 2.22 Å. Both Bi(1)-O(1) bond lengths are 2.33 Å. There is one shorter (2.42 Å) and one longer (2.55 Å) Bi(1)-O(3) bond length. There are three 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 distorted trigonal pyramidal geometry to two equivalent Li(1), one B(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Li(1), one B(1), and two equivalent Bi(1) atoms.