Li3VOF6 crystallizes in the orthorhombic P2_12_12_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 7-coordinate geometry to one O(1), one F(2), one F(4), two equivalent F(1), and two equivalent F(6) atoms. In the second Li site, Li(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form distorted LiOF6 pentagonal bipyramids that share corners with five equivalent V(1)OF6 pentagonal bipyramids and  an edgeedge with one V(1)OF6 pentagonal bipyramid. In the third Li site, Li(3) is bonded in a 7-coordinate geometry to one O(1), one F(2), one F(4), two equivalent F(3), and two equivalent F(5) atoms. V(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form VOF6 pentagonal bipyramids that share corners with five equivalent Li(2)OF6 pentagonal bipyramids and  an edgeedge with one Li(2)OF6 pentagonal bipyramid. O(1) is bonded in a 1-coordinate geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(1), and one V(1) atom to form a mixture of corner and edge-sharing FLi3V tetrahedra. In the second F site, F(2) is bonded in a 4-coordinate 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 4-coordinate geometry to one Li(2), two equivalent Li(3), and one V(1) atom. In the fourth F site, F(4) 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. In the fifth F site, F(5) is bonded to one Li(2), two equivalent Li(3), and one V(1) atom to form a mixture of distorted corner and edge-sharing FLi3V tetrahedra. In the sixth F site, F(6) is bonded to one Li(2), two equivalent Li(1), and one V(1) atom to form a mixture of distorted corner and edge-sharing FLi3V tetrahedra.
Li3VOF6 crystallizes in the orthorhombic P2_12_12_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 7-coordinate geometry to one O(1), one F(2), one F(4), two equivalent F(1), and two equivalent F(6) atoms. The Li(1)-O(1) bond length is 2.46 Å. The Li(1)-F(2) bond length is 2.43 Å. The Li(1)-F(4) bond length is 2.18 Å. There is one shorter (2.07 Å) and one longer (2.10 Å) Li(1)-F(1) bond length. There is one shorter (1.99 Å) and one longer (2.24 Å) Li(1)-F(6) bond length. In the second Li site, Li(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form distorted LiOF6 pentagonal bipyramids that share corners with five equivalent V(1)OF6 pentagonal bipyramids and  an edgeedge with one V(1)OF6 pentagonal bipyramid. The Li(2)-O(1) bond length is 2.19 Å. The Li(2)-F(1) bond length is 2.16 Å. The Li(2)-F(2) bond length is 1.92 Å. The Li(2)-F(3) bond length is 2.42 Å. The Li(2)-F(4) bond length is 2.21 Å. The Li(2)-F(5) bond length is 2.32 Å. The Li(2)-F(6) bond length is 2.26 Å. In the third Li site, Li(3) is bonded in a 7-coordinate geometry to one O(1), one F(2), one F(4), two equivalent F(3), and two equivalent F(5) atoms. The Li(3)-O(1) bond length is 2.56 Å. The Li(3)-F(2) bond length is 2.20 Å. The Li(3)-F(4) bond length is 2.30 Å. There is one shorter (2.00 Å) and one longer (2.23 Å) Li(3)-F(3) bond length. There is one shorter (2.03 Å) and one longer (2.07 Å) Li(3)-F(5) bond length. V(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form VOF6 pentagonal bipyramids that share corners with five equivalent Li(2)OF6 pentagonal bipyramids and  an edgeedge with one Li(2)OF6 pentagonal bipyramid. The V(1)-O(1) bond length is 1.63 Å. The V(1)-F(1) bond length is 2.03 Å. The V(1)-F(2) bond length is 2.00 Å. The V(1)-F(3) bond length is 1.93 Å. The V(1)-F(4) bond length is 1.93 Å. The V(1)-F(5) bond length is 2.04 Å. The V(1)-F(6) bond length is 1.98 Å. O(1) is bonded in a 1-coordinate geometry to one Li(1), one Li(2), one Li(3), and one V(1) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded to one Li(2), two equivalent Li(1), and one V(1) atom to form a mixture of corner and edge-sharing FLi3V tetrahedra. In the second F site, F(2) is bonded in a 4-coordinate 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 4-coordinate geometry to one Li(2), two equivalent Li(3), and one V(1) atom. In the fourth F site, F(4) 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. In the fifth F site, F(5) is bonded to one Li(2), two equivalent Li(3), and one V(1) atom to form a mixture of distorted corner and edge-sharing FLi3V tetrahedra. In the sixth F site, F(6) is bonded to one Li(2), two equivalent Li(1), and one V(1) atom to form a mixture of distorted corner and edge-sharing FLi3V tetrahedra.