Bi3O4F crystallizes in the monoclinic C2 space group. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(4), and one F(1) atom. In the second Bi site, Bi(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form distorted edge-sharing BiO6 octahedra. In the third Bi site, Bi(3) is bonded in a rectangular see-saw-like geometry to one O(2), one O(3), one O(4), and one F(1) atom. In the fourth Bi site, Bi(4) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted edge-sharing BiO6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Bi(1), one Bi(2), and one Bi(4) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Bi(1), one Bi(3), and one Bi(4) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Bi(2), one Bi(3), and one Bi(4) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Bi(1), one Bi(2), and one Bi(3) atom. F(1) is bonded in a linear geometry to one Bi(1) and one Bi(3) atom.
Bi3O4F crystallizes in the monoclinic C2 space group. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(4), and one F(1) atom. The Bi(1)-O(1) bond length is 2.12 Å. The Bi(1)-O(2) bond length is 2.22 Å. The Bi(1)-O(4) bond length is 2.12 Å. The Bi(1)-F(1) bond length is 2.49 Å. In the second Bi site, Bi(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form distorted edge-sharing BiO6 octahedra. Both Bi(2)-O(1) bond lengths are 2.29 Å. Both Bi(2)-O(3) bond lengths are 2.36 Å. Both Bi(2)-O(4) bond lengths are 2.63 Å. In the third Bi site, Bi(3) is bonded in a rectangular see-saw-like geometry to one O(2), one O(3), one O(4), and one F(1) atom. The Bi(3)-O(2) bond length is 2.13 Å. The Bi(3)-O(3) bond length is 2.12 Å. The Bi(3)-O(4) bond length is 2.21 Å. The Bi(3)-F(1) bond length is 2.50 Å. In the fourth Bi site, Bi(4) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted edge-sharing BiO6 octahedra. Both Bi(4)-O(1) bond lengths are 2.36 Å. Both Bi(4)-O(2) bond lengths are 2.63 Å. Both Bi(4)-O(3) bond lengths are 2.30 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Bi(1), one Bi(2), and one Bi(4) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Bi(1), one Bi(3), and one Bi(4) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Bi(2), one Bi(3), and one Bi(4) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Bi(1), one Bi(2), and one Bi(3) atom. F(1) is bonded in a linear geometry to one Bi(1) and one Bi(3) atom.