Nb3O2F5 crystallizes in the orthorhombic Pnnm space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to two equivalent O(1), one F(2), one F(3), and two equivalent F(1) atoms to form edge-sharing NbO2F4 octahedra. In the second Nb site, Nb(2) is bonded to two equivalent O(1), one F(2), one F(3), one F(4), and one F(5) atom to form a mixture of distorted corner and edge-sharing NbO2F4 octahedra. The corner-sharing octahedral tilt angles are 14°. O(1) is bonded in a distorted T-shaped geometry to one Nb(1) and two equivalent Nb(2) atoms. There are five inequivalent F sites. In the first F site, F(1) is bonded in a water-like geometry to two equivalent Nb(1) atoms. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Nb(1) and two equivalent Nb(2) atoms. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Nb(1) and two equivalent Nb(2) atoms. In the fourth F site, F(4) is bonded in an L-shaped geometry to two equivalent Nb(2) atoms. In the fifth F site, F(5) is bonded in a water-like geometry to two equivalent Nb(2) atoms.
Nb3O2F5 crystallizes in the orthorhombic Pnnm space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to two equivalent O(1), one F(2), one F(3), and two equivalent F(1) atoms to form edge-sharing NbO2F4 octahedra. Both Nb(1)-O(1) bond lengths are 2.03 Å. The Nb(1)-F(2) bond length is 2.26 Å. The Nb(1)-F(3) bond length is 2.29 Å. Both Nb(1)-F(1) bond lengths are 2.14 Å. In the second Nb site, Nb(2) is bonded to two equivalent O(1), one F(2), one F(3), one F(4), and one F(5) atom to form a mixture of distorted corner and edge-sharing NbO2F4 octahedra. The corner-sharing octahedral tilt angles are 14°. There is one shorter (2.04 Å) and one longer (2.10 Å) Nb(2)-O(1) bond length. The Nb(2)-F(2) bond length is 2.19 Å. The Nb(2)-F(3) bond length is 2.27 Å. The Nb(2)-F(4) bond length is 2.09 Å. The Nb(2)-F(5) bond length is 2.14 Å. O(1) is bonded in a distorted T-shaped geometry to one Nb(1) and two equivalent Nb(2) atoms. There are five inequivalent F sites. In the first F site, F(1) is bonded in a water-like geometry to two equivalent Nb(1) atoms. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Nb(1) and two equivalent Nb(2) atoms. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Nb(1) and two equivalent Nb(2) atoms. In the fourth F site, F(4) is bonded in an L-shaped geometry to two equivalent Nb(2) atoms. In the fifth F site, F(5) is bonded in a water-like geometry to two equivalent Nb(2) atoms.