Bi3O4F crystallizes in the monoclinic C2/c space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a rectangular see-saw-like geometry to one O(1), two equivalent O(2), and one F(1) atom. In the second Bi site, Bi(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted edge-sharing BiO6 octahedra. There are two 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(2) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Bi(2) and two equivalent Bi(1) atoms. F(1) is bonded in a linear geometry to two equivalent Bi(1) atoms.
Bi3O4F crystallizes in the monoclinic C2/c space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a rectangular see-saw-like geometry to one O(1), two equivalent O(2), and one F(1) atom. The Bi(1)-O(1) bond length is 2.12 Å. There is one shorter (2.13 Å) and one longer (2.21 Å) Bi(1)-O(2) bond length. The Bi(1)-F(1) bond length is 2.50 Å. In the second Bi site, Bi(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted edge-sharing BiO6 octahedra. Both Bi(2)-O(2) bond lengths are 2.63 Å. There are two shorter (2.27 Å) and two longer (2.38 Å) Bi(2)-O(1) bond lengths. There are two 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(2) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Bi(2) and two equivalent Bi(1) atoms. F(1) is bonded in a linear geometry to two equivalent Bi(1) atoms.