LiVSO4F3 crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(3), one O(5), one O(7), one F(3), and one F(6) atom. In the second Li site, Li(2) is bonded in a distorted trigonal non-coplanar geometry to one O(6), one F(1), and one F(4) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(8), one F(1), one F(2), one F(5), and one F(6) atom to form VO2F4 octahedra that share corners with two equivalent V(2)O2F4 octahedra,  a cornercorner with one S(1)O4 tetrahedra, and  a cornercorner with one S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-52°. In the second V site, V(2) is bonded to one O(4), one O(5), one F(2), one F(3), one F(4), and one F(5) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O2F4 octahedra,  a cornercorner with one S(1)O4 tetrahedra, and  a cornercorner with one S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-52°. There are two inequivalent S sites. In the first S site, 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 range from 48-49°. In the second S site, S(2) is bonded to one O(5), one O(6), one O(7), and one O(8) 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 51°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one V(1) and one S(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one S(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Li(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(2) and one S(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one S(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Li(2) and one S(2) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Li(1) and one S(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one V(1) and one S(2) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to 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. In the fourth F site, F(4) is bonded in a bent 120 degrees geometry to one Li(2) and one V(2) atom. In the fifth F site, F(5) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the sixth F site, F(6) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one V(1) atom.
LiVSO4F3 crystallizes in the monoclinic Pc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(3), one O(5), one O(7), one F(3), and one F(6) atom. The Li(1)-O(3) bond length is 2.61 Å. The Li(1)-O(5) bond length is 2.55 Å. The Li(1)-O(7) bond length is 1.96 Å. The Li(1)-F(3) bond length is 1.96 Å. The Li(1)-F(6) bond length is 2.18 Å. In the second Li site, Li(2) is bonded in a distorted trigonal non-coplanar geometry to one O(6), one F(1), and one F(4) atom. The Li(2)-O(6) bond length is 1.95 Å. The Li(2)-F(1) bond length is 1.97 Å. The Li(2)-F(4) bond length is 2.09 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(8), one F(1), one F(2), one F(5), and one F(6) atom to form VO2F4 octahedra that share corners with two equivalent V(2)O2F4 octahedra,  a cornercorner with one S(1)O4 tetrahedra, and  a cornercorner with one S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-52°. The V(1)-O(1) bond length is 1.91 Å. The V(1)-O(8) bond length is 2.00 Å. The V(1)-F(1) bond length is 1.84 Å. The V(1)-F(2) bond length is 1.94 Å. The V(1)-F(5) bond length is 1.97 Å. The V(1)-F(6) bond length is 1.81 Å. In the second V site, V(2) is bonded to one O(4), one O(5), one F(2), one F(3), one F(4), and one F(5) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O2F4 octahedra,  a cornercorner with one S(1)O4 tetrahedra, and  a cornercorner with one S(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-52°. The V(2)-O(4) bond length is 1.91 Å. The V(2)-O(5) bond length is 2.01 Å. The V(2)-F(2) bond length is 1.94 Å. The V(2)-F(3) bond length is 1.84 Å. The V(2)-F(4) bond length is 1.81 Å. The V(2)-F(5) bond length is 1.97 Å. There are two inequivalent S sites. In the first S site, 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 range from 48-49°. The S(1)-O(1) bond length is 1.56 Å. The S(1)-O(2) bond length is 1.44 Å. The S(1)-O(3) bond length is 1.45 Å. The S(1)-O(4) bond length is 1.56 Å. In the second S site, S(2) is bonded to one O(5), one O(6), one O(7), and one O(8) 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 51°. The S(2)-O(5) bond length is 1.53 Å. The S(2)-O(6) bond length is 1.46 Å. The S(2)-O(7) bond length is 1.46 Å. The S(2)-O(8) bond length is 1.53 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one V(1) and one S(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one S(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Li(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(2) and one S(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one S(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Li(2) and one S(2) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Li(1) and one S(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one V(1) and one S(2) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to 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. In the fourth F site, F(4) is bonded in a bent 120 degrees geometry to one Li(2) and one V(2) atom. In the fifth F site, F(5) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the sixth F site, F(6) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one V(1) atom.