Bi6O5F8 crystallizes in the triclinic P1 space group. There are six inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 7-coordinate geometry to one O(3), one O(4), two equivalent O(2), one F(5), one F(6), and one F(8) atom. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to one O(3), one O(5), one F(2), one F(6), two equivalent F(1), and two equivalent F(4) atoms. In the third Bi site, Bi(3) is bonded in a 7-coordinate geometry to one O(4), one O(5), two equivalent O(1), one F(3), one F(7), and one F(8) atom. In the fourth Bi site, Bi(4) is bonded in a 7-coordinate geometry to one O(1), two equivalent O(5), one F(1), one F(2), one F(3), and one F(7) atom. In the fifth Bi site, Bi(5) is bonded in a 6-coordinate geometry to one O(2), two equivalent O(3), one F(1), one F(5), and one F(6) atom. In the sixth Bi site, Bi(6) is bonded in a 7-coordinate geometry to one O(1), one O(2), two equivalent O(4), one F(3), one F(5), and one F(8) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Bi(4), one Bi(6), and two equivalent Bi(3) atoms to form OBi4 tetrahedra that share  a cornercorner with one O(2)Bi4 tetrahedra,  a cornercorner with one F(1)Bi4 tetrahedra, corners with two equivalent O(1)Bi4 tetrahedra, edges with two equivalent O(4)Bi4 tetrahedra, and edges with two equivalent O(5)Bi4 tetrahedra. In the second O site, O(2) is bonded to one Bi(5), one Bi(6), and two equivalent Bi(1) atoms to form OBi4 tetrahedra that share  a cornercorner with one O(1)Bi4 tetrahedra,  a cornercorner with one F(1)Bi4 tetrahedra, corners with two equivalent O(2)Bi4 tetrahedra, edges with two equivalent O(3)Bi4 tetrahedra, and edges with two equivalent O(4)Bi4 tetrahedra. In the third O site, O(3) is bonded to one Bi(1), one Bi(2), and two equivalent Bi(5) atoms to form OBi4 tetrahedra that share  a cornercorner with one O(4)Bi4 tetrahedra,  a cornercorner with one O(5)Bi4 tetrahedra, corners with two equivalent O(3)Bi4 tetrahedra, edges with two equivalent O(2)Bi4 tetrahedra, and edges with two equivalent F(1)Bi4 tetrahedra. In the fourth O site, O(4) is bonded to one Bi(1), one Bi(3), and two equivalent Bi(6) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fifth O site, O(5) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(4) atoms to form OBi4 tetrahedra that share  a cornercorner with one O(3)Bi4 tetrahedra,  a cornercorner with one O(4)Bi4 tetrahedra, corners with two equivalent O(5)Bi4 tetrahedra, edges with two equivalent O(1)Bi4 tetrahedra, and edges with two equivalent F(1)Bi4 tetrahedra. There are eight inequivalent F sites. In the first F site, F(1) is bonded to one Bi(4), one Bi(5), and two equivalent Bi(2) atoms to form distorted FBi4 tetrahedra that share  a cornercorner with one O(1)Bi4 tetrahedra,  a cornercorner with one O(2)Bi4 tetrahedra, corners with two equivalent F(1)Bi4 tetrahedra, edges with two equivalent O(3)Bi4 tetrahedra, and edges with two equivalent O(5)Bi4 tetrahedra. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Bi(2) and one Bi(4) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Bi(3), one Bi(4), and one Bi(6) atom. In the fourth F site, F(4) is bonded in a distorted bent 120 degrees geometry to two equivalent Bi(2) atoms. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Bi(1), one Bi(5), and one Bi(6) atom. In the sixth F site, F(6) is bonded in a trigonal non-coplanar geometry to one Bi(1), one Bi(2), and one Bi(5) atom. In the seventh F site, F(7) is bonded in a distorted bent 150 degrees geometry to one Bi(3) and one Bi(4) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Bi(1), one Bi(3), and one Bi(6) atom.
Bi6O5F8 crystallizes in the triclinic P1 space group. There are six inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 7-coordinate geometry to one O(3), one O(4), two equivalent O(2), one F(5), one F(6), and one F(8) atom. The Bi(1)-O(3) bond length is 2.30 Å. The Bi(1)-O(4) bond length is 2.33 Å. There is one shorter (2.35 Å) and one longer (2.36 Å) Bi(1)-O(2) bond length. The Bi(1)-F(5) bond length is 2.70 Å. The Bi(1)-F(6) bond length is 2.64 Å. The Bi(1)-F(8) bond length is 2.60 Å. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to one O(3), one O(5), one F(2), one F(6), two equivalent F(1), and two equivalent F(4) atoms. The Bi(2)-O(3) bond length is 2.63 Å. The Bi(2)-O(5) bond length is 2.50 Å. The Bi(2)-F(2) bond length is 2.19 Å. The Bi(2)-F(6) bond length is 2.42 Å. There is one shorter (2.63 Å) and one longer (2.65 Å) Bi(2)-F(1) bond length. There is one shorter (2.21 Å) and one longer (2.38 Å) Bi(2)-F(4) bond length. In the third Bi site, Bi(3) is bonded in a 7-coordinate geometry to one O(4), one O(5), two equivalent O(1), one F(3), one F(7), and one F(8) atom. The Bi(3)-O(4) bond length is 2.47 Å. The Bi(3)-O(5) bond length is 2.36 Å. There is one shorter (2.41 Å) and one longer (2.42 Å) Bi(3)-O(1) bond length. The Bi(3)-F(3) bond length is 2.39 Å. The Bi(3)-F(7) bond length is 2.42 Å. The Bi(3)-F(8) bond length is 2.60 Å. In the fourth Bi site, Bi(4) is bonded in a 7-coordinate geometry to one O(1), two equivalent O(5), one F(1), one F(2), one F(3), and one F(7) atom. The Bi(4)-O(1) bond length is 2.30 Å. There is one shorter (2.35 Å) and one longer (2.67 Å) Bi(4)-O(5) bond length. The Bi(4)-F(1) bond length is 2.49 Å. The Bi(4)-F(2) bond length is 2.56 Å. The Bi(4)-F(3) bond length is 2.65 Å. The Bi(4)-F(7) bond length is 2.24 Å. In the fifth Bi site, Bi(5) is bonded in a 6-coordinate geometry to one O(2), two equivalent O(3), one F(1), one F(5), and one F(6) atom. The Bi(5)-O(2) bond length is 2.31 Å. There is one shorter (2.31 Å) and one longer (2.44 Å) Bi(5)-O(3) bond length. The Bi(5)-F(1) bond length is 2.47 Å. The Bi(5)-F(5) bond length is 2.35 Å. The Bi(5)-F(6) bond length is 2.48 Å. In the sixth Bi site, Bi(6) is bonded in a 7-coordinate geometry to one O(1), one O(2), two equivalent O(4), one F(3), one F(5), and one F(8) atom. The Bi(6)-O(1) bond length is 2.36 Å. The Bi(6)-O(2) bond length is 2.43 Å. There is one shorter (2.34 Å) and one longer (2.44 Å) Bi(6)-O(4) bond length. The Bi(6)-F(3) bond length is 2.47 Å. The Bi(6)-F(5) bond length is 2.56 Å. The Bi(6)-F(8) bond length is 2.54 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Bi(4), one Bi(6), and two equivalent Bi(3) atoms to form OBi4 tetrahedra that share  a cornercorner with one O(2)Bi4 tetrahedra,  a cornercorner with one F(1)Bi4 tetrahedra, corners with two equivalent O(1)Bi4 tetrahedra, edges with two equivalent O(4)Bi4 tetrahedra, and edges with two equivalent O(5)Bi4 tetrahedra. In the second O site, O(2) is bonded to one Bi(5), one Bi(6), and two equivalent Bi(1) atoms to form OBi4 tetrahedra that share  a cornercorner with one O(1)Bi4 tetrahedra,  a cornercorner with one F(1)Bi4 tetrahedra, corners with two equivalent O(2)Bi4 tetrahedra, edges with two equivalent O(3)Bi4 tetrahedra, and edges with two equivalent O(4)Bi4 tetrahedra. In the third O site, O(3) is bonded to one Bi(1), one Bi(2), and two equivalent Bi(5) atoms to form OBi4 tetrahedra that share  a cornercorner with one O(4)Bi4 tetrahedra,  a cornercorner with one O(5)Bi4 tetrahedra, corners with two equivalent O(3)Bi4 tetrahedra, edges with two equivalent O(2)Bi4 tetrahedra, and edges with two equivalent F(1)Bi4 tetrahedra. In the fourth O site, O(4) is bonded to one Bi(1), one Bi(3), and two equivalent Bi(6) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fifth O site, O(5) is bonded to one Bi(2), one Bi(3), and two equivalent Bi(4) atoms to form OBi4 tetrahedra that share  a cornercorner with one O(3)Bi4 tetrahedra,  a cornercorner with one O(4)Bi4 tetrahedra, corners with two equivalent O(5)Bi4 tetrahedra, edges with two equivalent O(1)Bi4 tetrahedra, and edges with two equivalent F(1)Bi4 tetrahedra. There are eight inequivalent F sites. In the first F site, F(1) is bonded to one Bi(4), one Bi(5), and two equivalent Bi(2) atoms to form distorted FBi4 tetrahedra that share  a cornercorner with one O(1)Bi4 tetrahedra,  a cornercorner with one O(2)Bi4 tetrahedra, corners with two equivalent F(1)Bi4 tetrahedra, edges with two equivalent O(3)Bi4 tetrahedra, and edges with two equivalent O(5)Bi4 tetrahedra. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Bi(2) and one Bi(4) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Bi(3), one Bi(4), and one Bi(6) atom. In the fourth F site, F(4) is bonded in a distorted bent 120 degrees geometry to two equivalent Bi(2) atoms. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Bi(1), one Bi(5), and one Bi(6) atom. In the sixth F site, F(6) is bonded in a trigonal non-coplanar geometry to one Bi(1), one Bi(2), and one Bi(5) atom. In the seventh F site, F(7) is bonded in a distorted bent 150 degrees geometry to one Bi(3) and one Bi(4) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Bi(1), one Bi(3), and one Bi(6) atom.