Li4VF6 crystallizes in the monoclinic Cc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted see-saw-like geometry to one F(1), one F(2), one F(4), and one F(6) atom. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), and one F(6) atom to form LiF4 tetrahedra that share corners with four equivalent V(1)F6 octahedra and corners with two equivalent Li(4)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-55°. In the third Li site, Li(3) is bonded in a distorted see-saw-like geometry to one F(2), one F(4), one F(5), and one F(6) atom. In the fourth Li site, Li(4) is bonded to one F(1), one F(3), one F(4), and one F(5) atom to form distorted LiF4 tetrahedra that share corners with two equivalent Li(2)F4 tetrahedra and edges with two equivalent V(1)F6 octahedra. V(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form VF6 octahedra that share corners with four equivalent Li(2)F4 tetrahedra and edges with two equivalent Li(4)F4 tetrahedra. There are six inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one V(1) atom. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Li(4), and one V(1) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(3), one Li(4), and one V(1) atom to form a mixture of corner and edge-sharing FLi3V trigonal pyramids. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Li(3), one Li(4), and one V(1) atom. In the sixth F site, F(6) is bonded to one Li(1), one Li(2), one Li(3), and one V(1) atom to form a mixture of distorted corner and edge-sharing FLi3V trigonal pyramids.
Li4VF6 crystallizes in the monoclinic Cc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted see-saw-like geometry to one F(1), one F(2), one F(4), and one F(6) atom. The Li(1)-F(1) bond length is 2.01 Å. The Li(1)-F(2) bond length is 2.17 Å. The Li(1)-F(4) bond length is 1.96 Å. The Li(1)-F(6) bond length is 1.88 Å. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), and one F(6) atom to form LiF4 tetrahedra that share corners with four equivalent V(1)F6 octahedra and corners with two equivalent Li(4)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-55°. The Li(2)-F(1) bond length is 1.90 Å. The Li(2)-F(2) bond length is 1.94 Å. The Li(2)-F(3) bond length is 1.88 Å. The Li(2)-F(6) bond length is 1.88 Å. In the third Li site, Li(3) is bonded in a distorted see-saw-like geometry to one F(2), one F(4), one F(5), and one F(6) atom. The Li(3)-F(2) bond length is 1.96 Å. The Li(3)-F(4) bond length is 1.95 Å. The Li(3)-F(5) bond length is 1.91 Å. The Li(3)-F(6) bond length is 2.13 Å. In the fourth Li site, Li(4) is bonded to one F(1), one F(3), one F(4), and one F(5) atom to form distorted LiF4 tetrahedra that share corners with two equivalent Li(2)F4 tetrahedra and edges with two equivalent V(1)F6 octahedra. The Li(4)-F(1) bond length is 2.00 Å. The Li(4)-F(3) bond length is 1.89 Å. The Li(4)-F(4) bond length is 1.94 Å. The Li(4)-F(5) bond length is 1.90 Å. V(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form VF6 octahedra that share corners with four equivalent Li(2)F4 tetrahedra and edges with two equivalent Li(4)F4 tetrahedra. The V(1)-F(1) bond length is 2.16 Å. The V(1)-F(2) bond length is 2.15 Å. The V(1)-F(3) bond length is 2.11 Å. The V(1)-F(4) bond length is 2.13 Å. The V(1)-F(5) bond length is 2.13 Å. The V(1)-F(6) bond length is 2.06 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one V(1) atom. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Li(4), and one V(1) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(3), one Li(4), and one V(1) atom to form a mixture of corner and edge-sharing FLi3V trigonal pyramids. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Li(3), one Li(4), and one V(1) atom. In the sixth F site, F(6) is bonded to one Li(1), one Li(2), one Li(3), and one V(1) atom to form a mixture of distorted corner and edge-sharing FLi3V trigonal pyramids.