Bi3O2F5 crystallizes in the monoclinic P2/c space group. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(2) atoms. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), one F(1), and one F(2) atom. In the third Bi site, Bi(3) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(3), one F(4), and two equivalent F(2) atoms. In the fourth Bi site, Bi(4) is bonded in a distorted pentagonal pyramidal geometry to two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Bi(1) and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded to one Bi(1), one Bi(3), and two equivalent Bi(2) atoms to form distorted corner-sharing OBi4 tetrahedra. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 120 degrees geometry to one Bi(2) and one Bi(3) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Bi(2) and two equivalent Bi(3) atoms. In the third F site, F(3) is bonded in a distorted bent 120 degrees geometry to one Bi(3) and one Bi(4) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Bi(3) and one Bi(4) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one Bi(4) atom.
Bi3O2F5 crystallizes in the monoclinic P2/c space group. There are four inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Bi(1)-O(1) bond lengths are 2.23 Å. Both Bi(1)-O(2) bond lengths are 2.31 Å. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), one F(1), and one F(2) atom. There is one shorter (2.21 Å) and one longer (2.33 Å) Bi(2)-O(1) bond length. There is one shorter (2.40 Å) and one longer (2.73 Å) Bi(2)-O(2) bond length. The Bi(2)-F(1) bond length is 2.30 Å. The Bi(2)-F(2) bond length is 2.61 Å. In the third Bi site, Bi(3) is bonded in a 6-coordinate geometry to one O(2), one F(1), one F(3), one F(4), and two equivalent F(2) atoms. The Bi(3)-O(2) bond length is 2.17 Å. The Bi(3)-F(1) bond length is 2.52 Å. The Bi(3)-F(3) bond length is 2.32 Å. The Bi(3)-F(4) bond length is 2.26 Å. There is one shorter (2.30 Å) and one longer (2.45 Å) Bi(3)-F(2) bond length. In the fourth Bi site, Bi(4) is bonded in a distorted pentagonal pyramidal geometry to two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms. Both Bi(4)-F(3) bond lengths are 2.31 Å. Both Bi(4)-F(4) bond lengths are 2.41 Å. Both Bi(4)-F(5) bond lengths are 2.21 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Bi(1) and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded to one Bi(1), one Bi(3), and two equivalent Bi(2) atoms to form distorted corner-sharing OBi4 tetrahedra. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 120 degrees geometry to one Bi(2) and one Bi(3) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Bi(2) and two equivalent Bi(3) atoms. In the third F site, F(3) is bonded in a distorted bent 120 degrees geometry to one Bi(3) and one Bi(4) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Bi(3) and one Bi(4) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one Bi(4) atom.