LiV2OF5 crystallizes in the trigonal P3_121 space group. Li(1) is bonded in a trigonal planar geometry to one O(1) and two equivalent F(2) atoms. V(1) is bonded to one O(1), one F(3), two equivalent F(1), and two equivalent F(2) atoms to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 30-42°. O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1) and two equivalent V(1) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms.
LiV2OF5 crystallizes in the trigonal P3_121 space group. Li(1) is bonded in a trigonal planar geometry to one O(1) and two equivalent F(2) atoms. The Li(1)-O(1) bond length is 1.93 Å. Both Li(1)-F(2) bond lengths are 1.94 Å. V(1) is bonded to one O(1), one F(3), two equivalent F(1), and two equivalent F(2) atoms to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 30-42°. The V(1)-O(1) bond length is 1.87 Å. The V(1)-F(3) bond length is 2.01 Å. Both V(1)-F(1) bond lengths are 2.02 Å. There is one shorter (2.03 Å) and one longer (2.09 Å) V(1)-F(2) bond length. O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1) and two equivalent V(1) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms.