Li2V4OF12 crystallizes in the triclinic P1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal non-coplanar geometry to one F(3), one F(4), and one F(7) atom. In the second Li site, Li(2) is bonded in a trigonal non-coplanar geometry to one F(10), one F(6), and one F(9) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(3), one F(6), and two equivalent F(2) atoms to form VOF5 octahedra that share  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(2)OF5 octahedra, corners with two equivalent V(1)OF5 octahedra, and  an edgeedge with one V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 1-30°. In the second V site, V(2) is bonded to one O(1), one F(10), one F(12), one F(4), and two equivalent F(5) atoms to form VOF5 octahedra that share  a cornercorner with one V(1)OF5 octahedra, corners with two equivalent V(2)OF5 octahedra,  an edgeedge with one V(4)F6 octahedra, and  an edgeedge with one V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 9-30°. In the third V site, V(3) is bonded to one O(1), one F(12), one F(3), one F(9), and two equivalent F(8) atoms to form VOF5 octahedra that share  a cornercorner with one V(4)F6 octahedra, corners with two equivalent V(3)OF5 octahedra,  an edgeedge with one V(1)OF5 octahedra, and  an edgeedge with one V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 7-15°. In the fourth V site, V(4) is bonded to one F(1), one F(10), one F(12), one F(7), and two equivalent F(11) atoms to form VF6 octahedra that share  a cornercorner with one V(1)OF5 octahedra,  a cornercorner with one V(3)OF5 octahedra, corners with two equivalent V(4)F6 octahedra, and  an edgeedge with one V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 4-15°. O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(2), and one V(3) atom. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one V(1) and one V(4) atom. In the second F site, F(2) is bonded in a linear geometry to two equivalent V(1) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the fourth F site, F(4) is bonded in a bent 120 degrees geometry to one Li(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a linear geometry to two equivalent V(2) atoms. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the seventh F site, F(7) is bonded in a bent 120 degrees geometry to one Li(1) and one V(4) atom. In the eighth F site, F(8) is bonded in a linear geometry to two equivalent V(3) atoms. In the ninth F site, F(9) is bonded in a distorted bent 150 degrees geometry to one Li(2) and one V(3) atom. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(4) atom. In the eleventh F site, F(11) is bonded in a linear geometry to two equivalent V(4) atoms. In the twelfth F site, F(12) is bonded in a T-shaped geometry to one V(2), one V(3), and one V(4) atom.
Li2V4OF12 crystallizes in the triclinic P1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal non-coplanar geometry to one F(3), one F(4), and one F(7) atom. The Li(1)-F(3) bond length is 1.89 Å. The Li(1)-F(4) bond length is 1.90 Å. The Li(1)-F(7) bond length is 1.90 Å. In the second Li site, Li(2) is bonded in a trigonal non-coplanar geometry to one F(10), one F(6), and one F(9) atom. The Li(2)-F(10) bond length is 1.96 Å. The Li(2)-F(6) bond length is 1.84 Å. The Li(2)-F(9) bond length is 1.87 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(3), one F(6), and two equivalent F(2) atoms to form VOF5 octahedra that share  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(2)OF5 octahedra, corners with two equivalent V(1)OF5 octahedra, and  an edgeedge with one V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 1-30°. The V(1)-O(1) bond length is 1.98 Å. The V(1)-F(1) bond length is 2.03 Å. The V(1)-F(3) bond length is 2.09 Å. The V(1)-F(6) bond length is 1.91 Å. There is one shorter (1.96 Å) and one longer (1.99 Å) V(1)-F(2) bond length. In the second V site, V(2) is bonded to one O(1), one F(10), one F(12), one F(4), and two equivalent F(5) atoms to form VOF5 octahedra that share  a cornercorner with one V(1)OF5 octahedra, corners with two equivalent V(2)OF5 octahedra,  an edgeedge with one V(4)F6 octahedra, and  an edgeedge with one V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 9-30°. The V(2)-O(1) bond length is 1.93 Å. The V(2)-F(10) bond length is 2.08 Å. The V(2)-F(12) bond length is 2.20 Å. The V(2)-F(4) bond length is 1.91 Å. There is one shorter (1.96 Å) and one longer (2.00 Å) V(2)-F(5) bond length. In the third V site, V(3) is bonded to one O(1), one F(12), one F(3), one F(9), and two equivalent F(8) atoms to form VOF5 octahedra that share  a cornercorner with one V(4)F6 octahedra, corners with two equivalent V(3)OF5 octahedra,  an edgeedge with one V(1)OF5 octahedra, and  an edgeedge with one V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 7-15°. The V(3)-O(1) bond length is 1.95 Å. The V(3)-F(12) bond length is 2.13 Å. The V(3)-F(3) bond length is 2.05 Å. The V(3)-F(9) bond length is 1.92 Å. There is one shorter (1.97 Å) and one longer (1.99 Å) V(3)-F(8) bond length. In the fourth V site, V(4) is bonded to one F(1), one F(10), one F(12), one F(7), and two equivalent F(11) atoms to form VF6 octahedra that share  a cornercorner with one V(1)OF5 octahedra,  a cornercorner with one V(3)OF5 octahedra, corners with two equivalent V(4)F6 octahedra, and  an edgeedge with one V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 4-15°. The V(4)-F(1) bond length is 1.95 Å. The V(4)-F(10) bond length is 2.05 Å. The V(4)-F(12) bond length is 2.05 Å. The V(4)-F(7) bond length is 1.89 Å. There is one shorter (1.97 Å) and one longer (1.99 Å) V(4)-F(11) bond length. O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(2), and one V(3) atom. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one V(1) and one V(4) atom. In the second F site, F(2) is bonded in a linear geometry to two equivalent V(1) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the fourth F site, F(4) is bonded in a bent 120 degrees geometry to one Li(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a linear geometry to two equivalent V(2) atoms. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the seventh F site, F(7) is bonded in a bent 120 degrees geometry to one Li(1) and one V(4) atom. In the eighth F site, F(8) is bonded in a linear geometry to two equivalent V(3) atoms. In the ninth F site, F(9) is bonded in a distorted bent 150 degrees geometry to one Li(2) and one V(3) atom. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(4) atom. In the eleventh F site, F(11) is bonded in a linear geometry to two equivalent V(4) atoms. In the twelfth F site, F(12) is bonded in a T-shaped geometry to one V(2), one V(3), and one V(4) atom.