Li3V2F12 crystallizes in the monoclinic Pc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(11), one F(12), one F(4), one F(7), and one F(8) atom. In the second Li site, Li(2) is bonded to one F(1), one F(12), one F(2), one F(5), one F(6), and one F(9) atom to form LiF6 octahedra that share corners with four equivalent V(1)F6 octahedra and  an edgeedge with one V(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 30-38°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one F(10), one F(11), one F(3), one F(4), one F(7), and one F(8) atom. There are two inequivalent V sites. In the first V site, 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)F6 octahedra. The corner-sharing octahedral tilt angles range from 30-38°. In the second V site, V(2) is bonded to one F(10), one F(11), one F(12), one F(7), one F(8), and one F(9) atom to form VF6 octahedra that share  an edgeedge with one Li(2)F6 octahedra. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Li(2) and one V(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(3) and one V(1) atom. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), and one V(1) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. 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 distorted T-shaped geometry to one Li(1), one Li(3), and one V(2) atom. In the eighth F site, F(8) is bonded in a T-shaped geometry to one Li(1), one Li(3), and one V(2) atom. In the ninth F site, F(9) is bonded in a water-like geometry to one Li(2) and one V(2) atom. In the tenth F site, F(10) is bonded in a water-like geometry to one Li(3) and one V(2) atom. In the eleventh F site, F(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one V(2) atom. In the twelfth F site, F(12) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one V(2) atom.
Li3V2F12 crystallizes in the monoclinic Pc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(11), one F(12), one F(4), one F(7), and one F(8) atom. The Li(1)-F(11) bond length is 1.92 Å. The Li(1)-F(12) bond length is 2.00 Å. The Li(1)-F(4) bond length is 2.32 Å. The Li(1)-F(7) bond length is 1.94 Å. The Li(1)-F(8) bond length is 2.10 Å. In the second Li site, Li(2) is bonded to one F(1), one F(12), one F(2), one F(5), one F(6), and one F(9) atom to form LiF6 octahedra that share corners with four equivalent V(1)F6 octahedra and  an edgeedge with one V(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 30-38°. The Li(2)-F(1) bond length is 2.16 Å. The Li(2)-F(12) bond length is 2.14 Å. The Li(2)-F(2) bond length is 2.02 Å. The Li(2)-F(5) bond length is 2.11 Å. The Li(2)-F(6) bond length is 2.15 Å. The Li(2)-F(9) bond length is 1.98 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one F(10), one F(11), one F(3), one F(4), one F(7), and one F(8) atom. The Li(3)-F(10) bond length is 1.94 Å. The Li(3)-F(11) bond length is 2.00 Å. The Li(3)-F(3) bond length is 2.02 Å. The Li(3)-F(4) bond length is 2.18 Å. The Li(3)-F(7) bond length is 2.42 Å. The Li(3)-F(8) bond length is 2.01 Å. There are two inequivalent V sites. In the first V site, 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)F6 octahedra. The corner-sharing octahedral tilt angles range from 30-38°. The V(1)-F(1) bond length is 1.83 Å. The V(1)-F(2) bond length is 1.82 Å. The V(1)-F(3) bond length is 1.81 Å. The V(1)-F(4) bond length is 1.83 Å. The V(1)-F(5) bond length is 1.81 Å. The V(1)-F(6) bond length is 1.80 Å. In the second V site, V(2) is bonded to one F(10), one F(11), one F(12), one F(7), one F(8), and one F(9) atom to form VF6 octahedra that share  an edgeedge with one Li(2)F6 octahedra. The V(2)-F(10) bond length is 1.84 Å. The V(2)-F(11) bond length is 1.93 Å. The V(2)-F(12) bond length is 1.93 Å. The V(2)-F(7) bond length is 1.88 Å. The V(2)-F(8) bond length is 1.90 Å. The V(2)-F(9) bond length is 1.83 Å. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Li(2) and one V(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(3) and one V(1) atom. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), and one V(1) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. 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 distorted T-shaped geometry to one Li(1), one Li(3), and one V(2) atom. In the eighth F site, F(8) is bonded in a T-shaped geometry to one Li(1), one Li(3), and one V(2) atom. In the ninth F site, F(9) is bonded in a water-like geometry to one Li(2) and one V(2) atom. In the tenth F site, F(10) is bonded in a water-like geometry to one Li(3) and one V(2) atom. In the eleventh F site, F(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one V(2) atom. In the twelfth F site, F(12) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one V(2) atom.