Bi2O3 crystallizes in the triclinic P1 space group. There are six inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(8), and three equivalent O(9) atoms to form distorted corner-sharing BiO5 trigonal bipyramids. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to two equivalent O(4) and three equivalent O(5) atoms. In the third Bi site, Bi(3) is bonded in a 5-coordinate geometry to two equivalent O(1) and three equivalent O(2) atoms. In the fourth Bi site, Bi(4) is bonded to one O(2), one O(4), and three equivalent O(3) atoms to form corner-sharing BiO5 trigonal bipyramids. In the fifth Bi site, Bi(5) is bonded to one O(5), one O(7), and three equivalent O(6) atoms to form corner-sharing BiO5 trigonal bipyramids. In the sixth Bi site, Bi(6) is bonded in a 5-coordinate geometry to two equivalent O(7) and three equivalent O(8) atoms. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Bi(1) and two equivalent Bi(3) atoms. In the second O site, O(2) is bonded to one Bi(4) and three equivalent Bi(3) atoms to form distorted corner-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded in a trigonal planar geometry to three equivalent Bi(4) atoms. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Bi(4) and two equivalent Bi(2) atoms. In the fifth O site, O(5) is bonded to one Bi(5) and three equivalent Bi(2) atoms to form distorted corner-sharing OBi4 tetrahedra. In the sixth O site, O(6) is bonded in a trigonal planar geometry to three equivalent Bi(5) atoms. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Bi(5) and two equivalent Bi(6) atoms. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Bi(1) and three equivalent Bi(6) atoms. In the ninth O site, O(9) is bonded in a trigonal planar geometry to three equivalent Bi(1) atoms.
Bi2O3 crystallizes in the triclinic P1 space group. There are six inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(8), and three equivalent O(9) atoms to form distorted corner-sharing BiO5 trigonal bipyramids. The Bi(1)-O(1) bond length is 2.26 Å. The Bi(1)-O(8) bond length is 2.66 Å. There are a spread of Bi(1)-O(9) bond distances ranging from 2.27-2.29 Å. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to two equivalent O(4) and three equivalent O(5) atoms. There is one shorter (2.28 Å) and one longer (2.39 Å) Bi(2)-O(4) bond length. There are a spread of Bi(2)-O(5) bond distances ranging from 2.20-2.75 Å. In the third Bi site, Bi(3) is bonded in a 5-coordinate geometry to two equivalent O(1) and three equivalent O(2) atoms. There is one shorter (2.28 Å) and one longer (2.39 Å) Bi(3)-O(1) bond length. There are a spread of Bi(3)-O(2) bond distances ranging from 2.24-2.73 Å. In the fourth Bi site, Bi(4) is bonded to one O(2), one O(4), and three equivalent O(3) atoms to form corner-sharing BiO5 trigonal bipyramids. The Bi(4)-O(2) bond length is 2.34 Å. The Bi(4)-O(4) bond length is 2.38 Å. There are a spread of Bi(4)-O(3) bond distances ranging from 2.23-2.34 Å. In the fifth Bi site, Bi(5) is bonded to one O(5), one O(7), and three equivalent O(6) atoms to form corner-sharing BiO5 trigonal bipyramids. The Bi(5)-O(5) bond length is 2.37 Å. The Bi(5)-O(7) bond length is 2.34 Å. There are a spread of Bi(5)-O(6) bond distances ranging from 2.24-2.31 Å. In the sixth Bi site, Bi(6) is bonded in a 5-coordinate geometry to two equivalent O(7) and three equivalent O(8) atoms. There is one shorter (2.26 Å) and one longer (2.40 Å) Bi(6)-O(7) bond length. There are a spread of Bi(6)-O(8) bond distances ranging from 2.21-2.81 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Bi(1) and two equivalent Bi(3) atoms. In the second O site, O(2) is bonded to one Bi(4) and three equivalent Bi(3) atoms to form distorted corner-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded in a trigonal planar geometry to three equivalent Bi(4) atoms. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Bi(4) and two equivalent Bi(2) atoms. In the fifth O site, O(5) is bonded to one Bi(5) and three equivalent Bi(2) atoms to form distorted corner-sharing OBi4 tetrahedra. In the sixth O site, O(6) is bonded in a trigonal planar geometry to three equivalent Bi(5) atoms. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Bi(5) and two equivalent Bi(6) atoms. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Bi(1) and three equivalent Bi(6) atoms. In the ninth O site, O(9) is bonded in a trigonal planar geometry to three equivalent Bi(1) atoms.