V3O2F5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to four equivalent O(1) and two equivalent F(3) atoms. In the second V site, V(2) is bonded in a 7-coordinate geometry to two equivalent O(1), two equivalent F(1), and three equivalent F(2) atoms. O(1) is bonded to two equivalent V(1) and two equivalent V(2) atoms to form a mixture of edge and corner-sharing OV4 tetrahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to two equivalent V(2) atoms. In the second F site, F(2) is bonded in a 3-coordinate geometry to three equivalent V(2) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms.
V3O2F5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to four equivalent O(1) and two equivalent F(3) atoms. There are two shorter (2.07 Å) and two longer (2.09 Å) V(1)-O(1) bond lengths. There is one shorter (2.01 Å) and one longer (2.06 Å) V(1)-F(3) bond length. In the second V site, V(2) is bonded in a 7-coordinate geometry to two equivalent O(1), two equivalent F(1), and three equivalent F(2) atoms. There is one shorter (2.05 Å) and one longer (2.09 Å) V(2)-O(1) bond length. There is one shorter (2.02 Å) and one longer (2.04 Å) V(2)-F(1) bond length. There are a spread of V(2)-F(2) bond distances ranging from 2.02-2.36 Å. O(1) is bonded to two equivalent V(1) and two equivalent V(2) atoms to form a mixture of edge and corner-sharing OV4 tetrahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to two equivalent V(2) atoms. In the second F site, F(2) is bonded in a 3-coordinate geometry to three equivalent V(2) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms.