Li3VF6 crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one F(1), one F(3), one F(4), and one F(5) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one F(1), one F(2), one F(5), and one F(6) atom. In the third Li site, Li(3) is bonded to one F(2), one F(3), one F(4), and one F(6) atom to form LiF4 tetrahedra that share corners with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 31-51°. 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(3)F4 tetrahedra. There are six inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to 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(1), one Li(3), and one V(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one V(1) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one V(1) atom.
Li3VF6 crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one F(1), one F(3), one F(4), and one F(5) atom. The Li(1)-F(1) bond length is 1.90 Å. The Li(1)-F(3) bond length is 2.18 Å. The Li(1)-F(4) bond length is 1.89 Å. The Li(1)-F(5) bond length is 1.93 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one F(1), one F(2), one F(5), and one F(6) atom. The Li(2)-F(1) bond length is 1.92 Å. The Li(2)-F(2) bond length is 2.00 Å. The Li(2)-F(5) bond length is 2.00 Å. The Li(2)-F(6) bond length is 1.95 Å. In the third Li site, Li(3) is bonded to one F(2), one F(3), one F(4), and one F(6) atom to form LiF4 tetrahedra that share corners with four equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 31-51°. The Li(3)-F(2) bond length is 1.91 Å. The Li(3)-F(3) bond length is 1.88 Å. The Li(3)-F(4) bond length is 1.88 Å. The Li(3)-F(6) bond length is 1.86 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(3)F4 tetrahedra. The V(1)-F(1) bond length is 2.03 Å. The V(1)-F(2) bond length is 1.99 Å. The V(1)-F(3) bond length is 1.97 Å. The V(1)-F(4) bond length is 1.96 Å. The V(1)-F(5) bond length is 1.98 Å. The V(1)-F(6) bond length is 2.01 Å. There are six inequivalent F sites. In the first F site, F(1) is bonded in a T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to 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(1), one Li(3), and one V(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one V(1) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one V(1) atom.