Bi3O2 is alpha bismuth trifluoride-like structured and crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to four equivalent Bi(2) and four equivalent O(1) atoms. In the second Bi site, Bi(2) is bonded in a body-centered cubic geometry to eight equivalent Bi(1) atoms. O(1) is bonded to four equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra.
Bi3O2 is alpha bismuth trifluoride-like structured and crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to four equivalent Bi(2) and four equivalent O(1) atoms. All Bi(1)-Bi(2) bond lengths are 3.61 Å. All Bi(1)-O(1) bond lengths are 2.35 Å. In the second Bi site, Bi(2) is bonded in a body-centered cubic geometry to eight equivalent Bi(1) atoms. O(1) is bonded to four equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra.