Li2V2OF6 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one F(1), one F(4), one F(5), and one F(6) atom. In the second Li site, Li(2) is bonded to two equivalent O(1), one F(1), one F(2), one F(5), and one F(6) atom to form distorted LiO2F4 octahedra that share  a cornercorner with one V(2)OF5 octahedra, corners with two equivalent V(1)OF5 octahedra,  an edgeedge with one Li(2)O2F4 octahedra,  an edgeedge with one V(1)OF5 octahedra, and edges with two equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 17-34°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(2), one F(4), and two equivalent F(3) atoms to form VOF5 octahedra that share  a cornercorner with one V(2)OF5 octahedra, corners with two equivalent Li(2)O2F4 octahedra,  an edgeedge with one Li(2)O2F4 octahedra,  an edgeedge with one V(1)OF5 octahedra, and edges with two equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 13-23°. In the second V site, V(2) is bonded to one O(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form VOF5 octahedra that share  a cornercorner with one Li(2)O2F4 octahedra,  a cornercorner with one V(1)OF5 octahedra, edges with two equivalent Li(2)O2F4 octahedra, and edges with two equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 13-34°. O(1) is bonded to two equivalent Li(2), one V(1), and one V(2) atom to form distorted edge-sharing OLi2V2 trigonal pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(2) atom. In the sixth F site, F(6) is bonded in a T-shaped geometry to one Li(1), one Li(2), and one V(2) atom.
Li2V2OF6 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one F(1), one F(4), one F(5), and one F(6) atom. The Li(1)-F(1) bond length is 1.93 Å. The Li(1)-F(4) bond length is 1.97 Å. The Li(1)-F(5) bond length is 1.98 Å. The Li(1)-F(6) bond length is 1.86 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), one F(1), one F(2), one F(5), and one F(6) atom to form distorted LiO2F4 octahedra that share  a cornercorner with one V(2)OF5 octahedra, corners with two equivalent V(1)OF5 octahedra,  an edgeedge with one Li(2)O2F4 octahedra,  an edgeedge with one V(1)OF5 octahedra, and edges with two equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 17-34°. There is one shorter (2.09 Å) and one longer (2.34 Å) Li(2)-O(1) bond length. The Li(2)-F(1) bond length is 2.24 Å. The Li(2)-F(2) bond length is 2.43 Å. The Li(2)-F(5) bond length is 1.96 Å. The Li(2)-F(6) bond length is 2.01 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(2), one F(4), and two equivalent F(3) atoms to form VOF5 octahedra that share  a cornercorner with one V(2)OF5 octahedra, corners with two equivalent Li(2)O2F4 octahedra,  an edgeedge with one Li(2)O2F4 octahedra,  an edgeedge with one V(1)OF5 octahedra, and edges with two equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 13-23°. The V(1)-O(1) bond length is 1.89 Å. The V(1)-F(1) bond length is 1.91 Å. The V(1)-F(2) bond length is 2.07 Å. The V(1)-F(4) bond length is 2.00 Å. There is one shorter (2.11 Å) and one longer (2.14 Å) V(1)-F(3) bond length. In the second V site, V(2) is bonded to one O(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form VOF5 octahedra that share  a cornercorner with one Li(2)O2F4 octahedra,  a cornercorner with one V(1)OF5 octahedra, edges with two equivalent Li(2)O2F4 octahedra, and edges with two equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 13-34°. The V(2)-O(1) bond length is 1.89 Å. The V(2)-F(2) bond length is 2.05 Å. The V(2)-F(3) bond length is 2.14 Å. The V(2)-F(4) bond length is 2.11 Å. The V(2)-F(5) bond length is 1.95 Å. The V(2)-F(6) bond length is 1.97 Å. O(1) is bonded to two equivalent Li(2), one V(1), and one V(2) atom to form distorted edge-sharing OLi2V2 trigonal pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(2) atom. In the sixth F site, F(6) is bonded in a T-shaped geometry to one Li(1), one Li(2), and one V(2) atom.