BiOF crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted body-centered cubic geometry to one O(2), one O(3), one F(3), two equivalent F(2), and three equivalent F(1) atoms. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to one O(4), three equivalent O(1), one F(2), one F(4), and two equivalent F(3) atoms. In the third Bi site, Bi(3) is bonded in a 7-coordinate geometry to one O(4), two equivalent O(3), one F(2), and three equivalent F(4) atoms. In the fourth Bi site, Bi(4) is bonded in a 7-coordinate geometry to one O(3), two equivalent O(4), three equivalent O(2), and one F(3) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to three equivalent Bi(2) atoms. In the second O site, O(2) is bonded to one Bi(1) and three equivalent Bi(4) atoms to form OBi4 tetrahedra that share corners with two equivalent O(2)Bi4 tetrahedra, corners with two equivalent F(2)Bi4 tetrahedra, corners with two equivalent F(3)Bi4 tetrahedra, corners with four equivalent O(3)Bi4 tetrahedra,  an edgeedge with one F(3)Bi4 tetrahedra, and edges with two equivalent O(2)Bi4 tetrahedra. In the third O site, O(3) is bonded to one Bi(1), one Bi(4), and two equivalent Bi(3) atoms to form OBi4 tetrahedra that share corners with two equivalent O(3)Bi4 tetrahedra, corners with two equivalent F(3)Bi4 tetrahedra, corners with four equivalent O(2)Bi4 tetrahedra, corners with four equivalent F(4)Bi4 tetrahedra,  an edgeedge with one F(4)Bi4 tetrahedra, and edges with two equivalent F(2)Bi4 tetrahedra. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Bi(2), one Bi(3), and two equivalent Bi(4) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Bi(1) atoms. In the second F site, F(2) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form distorted FBi4 tetrahedra that share corners with two equivalent O(2)Bi4 tetrahedra, corners with two equivalent F(2)Bi4 tetrahedra, corners with four equivalent F(4)Bi4 tetrahedra, edges with two equivalent O(3)Bi4 tetrahedra, and edges with two equivalent F(3)Bi4 tetrahedra. In the third F site, F(3) is bonded to one Bi(1), one Bi(4), and two equivalent Bi(2) atoms to form distorted FBi4 tetrahedra that share corners with two equivalent O(2)Bi4 tetrahedra, corners with two equivalent O(3)Bi4 tetrahedra, corners with two equivalent F(3)Bi4 tetrahedra, corners with two equivalent F(4)Bi4 tetrahedra,  an edgeedge with one O(2)Bi4 tetrahedra, and edges with two equivalent F(2)Bi4 tetrahedra. In the fourth F site, F(4) is bonded to one Bi(2) and three equivalent Bi(3) atoms to form distorted FBi4 tetrahedra that share corners with two equivalent F(3)Bi4 tetrahedra, corners with two equivalent F(4)Bi4 tetrahedra, corners with four equivalent O(3)Bi4 tetrahedra, corners with four equivalent F(2)Bi4 tetrahedra,  an edgeedge with one O(3)Bi4 tetrahedra, and edges with two equivalent F(4)Bi4 tetrahedra.
BiOF crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted body-centered cubic geometry to one O(2), one O(3), one F(3), two equivalent F(2), and three equivalent F(1) atoms. The Bi(1)-O(2) bond length is 2.19 Å. The Bi(1)-O(3) bond length is 2.70 Å. The Bi(1)-F(3) bond length is 2.33 Å. Both Bi(1)-F(2) bond lengths are 2.44 Å. There are two shorter (2.38 Å) and one longer (2.62 Å) Bi(1)-F(1) bond length. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to one O(4), three equivalent O(1), one F(2), one F(4), and two equivalent F(3) atoms. The Bi(2)-O(4) bond length is 2.81 Å. There is one shorter (2.27 Å) and two longer (2.29 Å) Bi(2)-O(1) bond lengths. The Bi(2)-F(2) bond length is 2.74 Å. The Bi(2)-F(4) bond length is 2.35 Å. Both Bi(2)-F(3) bond lengths are 2.72 Å. In the third Bi site, Bi(3) is bonded in a 7-coordinate geometry to one O(4), two equivalent O(3), one F(2), and three equivalent F(4) atoms. The Bi(3)-O(4) bond length is 2.18 Å. Both Bi(3)-O(3) bond lengths are 2.31 Å. The Bi(3)-F(2) bond length is 2.65 Å. There is one shorter (2.68 Å) and two longer (2.75 Å) Bi(3)-F(4) bond lengths. In the fourth Bi site, Bi(4) is bonded in a 7-coordinate geometry to one O(3), two equivalent O(4), three equivalent O(2), and one F(3) atom. The Bi(4)-O(3) bond length is 2.48 Å. Both Bi(4)-O(4) bond lengths are 2.41 Å. There is one shorter (2.53 Å) and two longer (2.55 Å) Bi(4)-O(2) bond lengths. The Bi(4)-F(3) bond length is 2.54 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to three equivalent Bi(2) atoms. In the second O site, O(2) is bonded to one Bi(1) and three equivalent Bi(4) atoms to form OBi4 tetrahedra that share corners with two equivalent O(2)Bi4 tetrahedra, corners with two equivalent F(2)Bi4 tetrahedra, corners with two equivalent F(3)Bi4 tetrahedra, corners with four equivalent O(3)Bi4 tetrahedra,  an edgeedge with one F(3)Bi4 tetrahedra, and edges with two equivalent O(2)Bi4 tetrahedra. In the third O site, O(3) is bonded to one Bi(1), one Bi(4), and two equivalent Bi(3) atoms to form OBi4 tetrahedra that share corners with two equivalent O(3)Bi4 tetrahedra, corners with two equivalent F(3)Bi4 tetrahedra, corners with four equivalent O(2)Bi4 tetrahedra, corners with four equivalent F(4)Bi4 tetrahedra,  an edgeedge with one F(4)Bi4 tetrahedra, and edges with two equivalent F(2)Bi4 tetrahedra. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Bi(2), one Bi(3), and two equivalent Bi(4) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Bi(1) atoms. In the second F site, F(2) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(1) atoms to form distorted FBi4 tetrahedra that share corners with two equivalent O(2)Bi4 tetrahedra, corners with two equivalent F(2)Bi4 tetrahedra, corners with four equivalent F(4)Bi4 tetrahedra, edges with two equivalent O(3)Bi4 tetrahedra, and edges with two equivalent F(3)Bi4 tetrahedra. In the third F site, F(3) is bonded to one Bi(1), one Bi(4), and two equivalent Bi(2) atoms to form distorted FBi4 tetrahedra that share corners with two equivalent O(2)Bi4 tetrahedra, corners with two equivalent O(3)Bi4 tetrahedra, corners with two equivalent F(3)Bi4 tetrahedra, corners with two equivalent F(4)Bi4 tetrahedra,  an edgeedge with one O(2)Bi4 tetrahedra, and edges with two equivalent F(2)Bi4 tetrahedra. In the fourth F site, F(4) is bonded to one Bi(2) and three equivalent Bi(3) atoms to form distorted FBi4 tetrahedra that share corners with two equivalent F(3)Bi4 tetrahedra, corners with two equivalent F(4)Bi4 tetrahedra, corners with four equivalent O(3)Bi4 tetrahedra, corners with four equivalent F(2)Bi4 tetrahedra,  an edgeedge with one O(3)Bi4 tetrahedra, and edges with two equivalent F(4)Bi4 tetrahedra.