LiBi3O5 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a distorted trigonal pyramidal geometry to one O(2), one O(3), and two equivalent O(1) atoms. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(1) atoms. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(1) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Bi(2), and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Bi(2), and two equivalent Bi(1) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Bi(2), and two equivalent Bi(1) atoms. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Bi(2) and two equivalent Bi(1) atoms.
LiBi3O5 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a distorted trigonal pyramidal geometry to one O(2), one O(3), and two equivalent O(1) atoms. The Li(1)-O(2) bond length is 2.03 Å. The Li(1)-O(3) bond length is 1.95 Å. Both Li(1)-O(1) bond lengths are 2.04 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(1) atoms. The Bi(1)-O(2) bond length is 2.33 Å. The Bi(1)-O(3) bond length is 2.38 Å. The Bi(1)-O(4) bond length is 2.23 Å. There is one shorter (2.33 Å) and one longer (2.51 Å) Bi(1)-O(1) bond length. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(1) atoms. The Bi(2)-O(2) bond length is 2.51 Å. The Bi(2)-O(3) bond length is 2.30 Å. The Bi(2)-O(4) bond length is 2.53 Å. Both Bi(2)-O(1) bond lengths are 2.33 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Bi(2), and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Bi(2), and two equivalent Bi(1) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Bi(2), and two equivalent Bi(1) atoms. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Bi(2) and two equivalent Bi(1) atoms.