Bi4O5 crystallizes in the monoclinic Cc space group. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted T-shaped geometry to one O(2), one O(3), and one O(4) atom. In the second Bi site, Bi(2) is bonded in a distorted see-saw-like geometry to one O(1), one O(4), and two equivalent O(3) atoms. In the third Bi site, Bi(3) is bonded in a 5-coordinate geometry to one O(4), two equivalent O(2), and two equivalent O(5) atoms. In the fourth Bi site, Bi(4) is bonded to one O(4), two equivalent O(1), and two equivalent O(5) atoms to form distorted edge-sharing BiO5 square pyramids. There are five inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Bi(2) and two equivalent Bi(4) atoms. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one Bi(1) and two equivalent Bi(3) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Bi(1) and two equivalent Bi(2) atoms. In the fourth O site, O(4) is bonded to one Bi(1), one Bi(2), one Bi(3), and one Bi(4) atom to form distorted corner-sharing OBi4 tetrahedra. In the fifth O site, O(5) is bonded to two equivalent Bi(3) and two equivalent Bi(4) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra.
Bi4O5 crystallizes in the monoclinic Cc space group. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted T-shaped geometry to one O(2), one O(3), and one O(4) atom. The Bi(1)-O(2) bond length is 2.20 Å. The Bi(1)-O(3) bond length is 2.38 Å. The Bi(1)-O(4) bond length is 2.38 Å. In the second Bi site, Bi(2) is bonded in a distorted see-saw-like geometry to one O(1), one O(4), and two equivalent O(3) atoms. The Bi(2)-O(1) bond length is 2.28 Å. The Bi(2)-O(4) bond length is 2.29 Å. There is one shorter (2.22 Å) and one longer (2.24 Å) Bi(2)-O(3) bond length. In the third Bi site, Bi(3) is bonded in a 5-coordinate geometry to one O(4), two equivalent O(2), and two equivalent O(5) atoms. The Bi(3)-O(4) bond length is 2.79 Å. There is one shorter (2.21 Å) and one longer (2.35 Å) Bi(3)-O(2) bond length. There is one shorter (2.35 Å) and one longer (2.38 Å) Bi(3)-O(5) bond length. In the fourth Bi site, Bi(4) is bonded to one O(4), two equivalent O(1), and two equivalent O(5) atoms to form distorted edge-sharing BiO5 square pyramids. The Bi(4)-O(4) bond length is 2.27 Å. There is one shorter (2.18 Å) and one longer (2.39 Å) Bi(4)-O(1) bond length. There is one shorter (2.28 Å) and one longer (2.56 Å) Bi(4)-O(5) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Bi(2) and two equivalent Bi(4) atoms. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one Bi(1) and two equivalent Bi(3) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Bi(1) and two equivalent Bi(2) atoms. In the fourth O site, O(4) is bonded to one Bi(1), one Bi(2), one Bi(3), and one Bi(4) atom to form distorted corner-sharing OBi4 tetrahedra. In the fifth O site, O(5) is bonded to two equivalent Bi(3) and two equivalent Bi(4) atoms to form a mixture of edge and corner-sharing OBi4 tetrahedra.