VMnO2F5 crystallizes in the orthorhombic Imma space group. V(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra and corners with four equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 36-40°. Mn(1) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form MnO2F4 octahedra that share corners with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles are 40°. O(1) is bonded in a single-bond geometry to one Mn(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(1) and one Mn(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms.
VMnO2F5 crystallizes in the orthorhombic Imma space group. V(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra and corners with four equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 36-40°. Both V(1)-F(2) bond lengths are 1.96 Å. All V(1)-F(1) bond lengths are 1.86 Å. Mn(1) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form MnO2F4 octahedra that share corners with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles are 40°. Both Mn(1)-O(1) bond lengths are 1.67 Å. All Mn(1)-F(1) bond lengths are 2.15 Å. O(1) is bonded in a single-bond geometry to one Mn(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(1) and one Mn(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms.