BiO2 crystallizes in the orthorhombic Imma space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form edge-sharing BiO6 octahedra. In the second Bi site, Bi(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted edge-sharing BiO6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Bi(2) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Bi(1) and two equivalent Bi(2) atoms.
BiO2 crystallizes in the orthorhombic Imma space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form edge-sharing BiO6 octahedra. Both Bi(1)-O(2) bond lengths are 2.12 Å. All Bi(1)-O(1) bond lengths are 2.21 Å. In the second Bi site, Bi(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted edge-sharing BiO6 octahedra. Both Bi(2)-O(1) bond lengths are 2.44 Å. All Bi(2)-O(2) bond lengths are 2.41 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Bi(2) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Bi(1) and two equivalent Bi(2) atoms.