Li2VSO4F3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), one F(1), and one F(3) atom. In the second Li site, Li(2) is bonded in a distorted T-shaped geometry to one O(2), one O(4), and one F(1) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form VO2F4 octahedra that share corners with two equivalent V(2)O2F4 octahedra and corners with two equivalent S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. In the second V site, V(2) is bonded to two equivalent O(4), two equivalent F(2), and two equivalent F(3) atoms to form VO2F4 octahedra that share corners with two equivalent V(1)O2F4 octahedra and corners with two equivalent S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share  a cornercorner with one V(1)O2F4 octahedra and  a cornercorner with one V(2)O2F4 octahedra. The corner-sharing octahedral tilt angles are 56°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one S(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Li(2) and one S(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Li(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one V(2), and one S(1) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(1) and one V(2) atom.
Li2VSO4F3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), one F(1), and one F(3) atom. The Li(1)-O(1) bond length is 2.39 Å. The Li(1)-O(3) bond length is 2.03 Å. The Li(1)-F(1) bond length is 2.56 Å. The Li(1)-F(3) bond length is 1.93 Å. In the second Li site, Li(2) is bonded in a distorted T-shaped geometry to one O(2), one O(4), and one F(1) atom. The Li(2)-O(2) bond length is 2.02 Å. The Li(2)-O(4) bond length is 2.29 Å. The Li(2)-F(1) bond length is 1.97 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form VO2F4 octahedra that share corners with two equivalent V(2)O2F4 octahedra and corners with two equivalent S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. Both V(1)-O(1) bond lengths are 2.04 Å. Both V(1)-F(1) bond lengths are 1.93 Å. Both V(1)-F(2) bond lengths are 2.02 Å. In the second V site, V(2) is bonded to two equivalent O(4), two equivalent F(2), and two equivalent F(3) atoms to form VO2F4 octahedra that share corners with two equivalent V(1)O2F4 octahedra and corners with two equivalent S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. Both V(2)-O(4) bond lengths are 2.07 Å. Both V(2)-F(2) bond lengths are 1.98 Å. Both V(2)-F(3) bond lengths are 1.92 Å. S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share  a cornercorner with one V(1)O2F4 octahedra and  a cornercorner with one V(2)O2F4 octahedra. The corner-sharing octahedral tilt angles are 56°. The S(1)-O(1) bond length is 1.53 Å. The S(1)-O(2) bond length is 1.46 Å. The S(1)-O(3) bond length is 1.47 Å. The S(1)-O(4) bond length is 1.52 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one S(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Li(2) and one S(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Li(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one V(2), and one S(1) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(1) and one V(2) atom.