Bi4O7 crystallizes in the tetragonal P-4b2 space group. Bi(1) is bonded in a 7-coordinate geometry to one O(1), one O(4), one O(5), two equivalent O(2), and two equivalent O(3) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded to four equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded to four equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fourth O site, O(4) is bonded to four equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fifth O site, O(5) is bonded to four equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra.
Bi4O7 crystallizes in the tetragonal P-4b2 space group. Bi(1) is bonded in a 7-coordinate geometry to one O(1), one O(4), one O(5), two equivalent O(2), and two equivalent O(3) atoms. The Bi(1)-O(1) bond length is 2.45 Å. The Bi(1)-O(4) bond length is 2.38 Å. The Bi(1)-O(5) bond length is 2.31 Å. There is one shorter (2.42 Å) and one longer (2.48 Å) Bi(1)-O(2) bond length. Both Bi(1)-O(3) bond lengths are 2.38 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded to four equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded to four equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fourth O site, O(4) is bonded to four equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fifth O site, O(5) is bonded to four equivalent Bi(1) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra.