Bi3O2F5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 7-coordinate geometry to two equivalent O(1), one F(1), two equivalent F(3), and three equivalent F(2) atoms. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to four equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms. O(1) is bonded to two equivalent Bi(1) and two equivalent Bi(2) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to two equivalent Bi(1) and two equivalent Bi(2) atoms. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Bi(1) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Bi(2) and two equivalent Bi(1) atoms.
Bi3O2F5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 7-coordinate geometry to two equivalent O(1), one F(1), two equivalent F(3), and three equivalent F(2) atoms. There is one shorter (2.23 Å) and one longer (2.34 Å) Bi(1)-O(1) bond length. The Bi(1)-F(1) bond length is 2.77 Å. There is one shorter (2.33 Å) and one longer (2.45 Å) Bi(1)-F(3) bond length. There are a spread of Bi(1)-F(2) bond distances ranging from 2.34-2.63 Å. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to four equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms. There are two shorter (2.32 Å) and two longer (2.37 Å) Bi(2)-O(1) bond lengths. There is one shorter (2.44 Å) and one longer (2.70 Å) Bi(2)-F(1) bond length. Both Bi(2)-F(3) bond lengths are 2.49 Å. O(1) is bonded to two equivalent Bi(1) and two equivalent Bi(2) atoms to form a mixture of corner and edge-sharing OBi4 tetrahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to two equivalent Bi(1) and two equivalent Bi(2) atoms. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Bi(1) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Bi(2) and two equivalent Bi(1) atoms.