BiO2 crystallizes in the trigonal R3m space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted tetrahedral geometry to one O(2), three equivalent O(1), and three equivalent O(4) atoms. In the second Bi site, Bi(2) is bonded in a distorted body-centered cubic geometry to one O(2), one O(3), three equivalent O(1), and three equivalent O(4) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Bi(1) and three equivalent Bi(2) atoms to form a mixture of distorted edge and corner-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded to one Bi(1) and three equivalent Bi(2) atoms to form a mixture of distorted edge and corner-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded in a trigonal planar geometry to three equivalent Bi(2) atoms. In the fourth O site, O(4) is bonded to one Bi(1) and three equivalent Bi(2) atoms to form a mixture of distorted edge and corner-sharing OBi4 tetrahedra.
BiO2 crystallizes in the trigonal R3m space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted tetrahedral geometry to one O(2), three equivalent O(1), and three equivalent O(4) atoms. The Bi(1)-O(2) bond length is 2.10 Å. All Bi(1)-O(1) bond lengths are 2.65 Å. All Bi(1)-O(4) bond lengths are 2.10 Å. In the second Bi site, Bi(2) is bonded in a distorted body-centered cubic geometry to one O(2), one O(3), three equivalent O(1), and three equivalent O(4) atoms. The Bi(2)-O(2) bond length is 2.51 Å. The Bi(2)-O(3) bond length is 2.28 Å. There is one shorter (2.33 Å) and two longer (2.36 Å) Bi(2)-O(1) bond lengths. There are two shorter (2.53 Å) and one longer (2.61 Å) Bi(2)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Bi(1) and three equivalent Bi(2) atoms to form a mixture of distorted edge and corner-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded to one Bi(1) and three equivalent Bi(2) atoms to form a mixture of distorted edge and corner-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded in a trigonal planar geometry to three equivalent Bi(2) atoms. In the fourth O site, O(4) is bonded to one Bi(1) and three equivalent Bi(2) atoms to form a mixture of distorted edge and corner-sharing OBi4 tetrahedra.