Bi2O3 is Chalcostibite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. In the second Bi site, Bi(2) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing BiO5 square pyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Bi(1) and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Bi(2) and two equivalent Bi(1) atoms. In the third O site, O(3) is bonded to two equivalent Bi(1) and two equivalent Bi(2) atoms to form corner-sharing OBi4 tetrahedra.
Bi2O3 is Chalcostibite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. There is one shorter (2.30 Å) and one longer (2.79 Å) Bi(1)-O(1) bond length. There is one shorter (2.16 Å) and one longer (2.40 Å) Bi(1)-O(2) bond length. There is one shorter (2.25 Å) and one longer (2.50 Å) Bi(1)-O(3) bond length. In the second Bi site, Bi(2) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing BiO5 square pyramids. The Bi(2)-O(2) bond length is 2.24 Å. There is one shorter (2.14 Å) and one longer (2.48 Å) Bi(2)-O(1) bond length. There is one shorter (2.24 Å) and one longer (2.57 Å) Bi(2)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Bi(1) and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Bi(2) and two equivalent Bi(1) atoms. In the third O site, O(3) is bonded to two equivalent Bi(1) and two equivalent Bi(2) atoms to form corner-sharing OBi4 tetrahedra.