Bi2O3 crystallizes in the trigonal P31c space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent O(1) and three equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing BiO5 square pyramids. In the second Bi site, Bi(2) is bonded in a 3-coordinate geometry to three equivalent O(1) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Bi(2) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to three equivalent Bi(1) atoms.
Bi2O3 crystallizes in the trigonal P31c space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent O(1) and three equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing BiO5 square pyramids. There is one shorter (2.38 Å) and one longer (2.41 Å) Bi(1)-O(1) bond length. There are a spread of Bi(1)-O(2) bond distances ranging from 2.14-2.39 Å. In the second Bi site, Bi(2) is bonded in a 3-coordinate geometry to three equivalent O(1) atoms. All Bi(2)-O(1) bond lengths are 2.15 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Bi(2) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to three equivalent Bi(1) atoms.