Bi3O4F crystallizes in the monoclinic P2/c space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(2), two equivalent O(1), and two equivalent F(1) atoms to form distorted BiO3F2 square pyramids that share corners with four equivalent Bi(2)O6 octahedra, corners with two equivalent Bi(1)O3F2 square pyramids, and edges with three equivalent Bi(1)O3F2 square pyramids. The corner-sharing octahedral tilt angles range from 49-64°. In the second Bi site, Bi(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted BiO6 octahedra that share corners with eight equivalent Bi(1)O3F2 square pyramids and edges with two equivalent Bi(2)O6 octahedra. There are two 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(1) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Bi(1) and two equivalent Bi(2) atoms. F(1) is bonded in a rectangular see-saw-like geometry to four equivalent Bi(1) atoms.
Bi3O4F crystallizes in the monoclinic P2/c space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(2), two equivalent O(1), and two equivalent F(1) atoms to form distorted BiO3F2 square pyramids that share corners with four equivalent Bi(2)O6 octahedra, corners with two equivalent Bi(1)O3F2 square pyramids, and edges with three equivalent Bi(1)O3F2 square pyramids. The corner-sharing octahedral tilt angles range from 49-64°. The Bi(1)-O(2) bond length is 2.16 Å. There is one shorter (2.13 Å) and one longer (2.17 Å) Bi(1)-O(1) bond length. There is one shorter (2.66 Å) and one longer (2.73 Å) Bi(1)-F(1) bond length. In the second Bi site, Bi(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted BiO6 octahedra that share corners with eight equivalent Bi(1)O3F2 square pyramids and edges with two equivalent Bi(2)O6 octahedra. Both Bi(2)-O(1) bond lengths are 2.63 Å. There are two shorter (2.26 Å) and two longer (2.36 Å) Bi(2)-O(2) 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(2) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Bi(1) and two equivalent Bi(2) atoms. F(1) is bonded in a rectangular see-saw-like geometry to four equivalent Bi(1) atoms.