LiVF4 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(4), one F(5), and one F(8) atom to form LiF4 tetrahedra that share corners with two equivalent V(1)F6 octahedra, corners with two equivalent V(2)F6 octahedra, and corners with two equivalent V(3)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 20-63°. In the second Li site, Li(2) is bonded to one F(10), one F(2), one F(3), and one F(9) atom to form LiF4 tetrahedra that share corners with two equivalent V(1)F6 octahedra, corners with three equivalent V(2)F6 octahedra, and  a cornercorner with one V(3)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 36-55°. In the third Li site, Li(3) is bonded to one F(11), one F(12), one F(6), and one F(7) atom to form LiF4 tetrahedra that share  a cornercorner with one V(2)F6 octahedra, corners with two equivalent V(1)F6 octahedra, and corners with two equivalent V(3)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 13-56°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one F(1), one F(11), one F(12), one F(4), and two equivalent F(3) atoms to form VF6 octahedra that share corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(2)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra,  an edgeedge with one V(1)F6 octahedra, and  an edgeedge with one V(3)F5 trigonal bipyramid. In the second V site, V(2) is bonded to one F(10), one F(2), one F(5), one F(6), one F(8), and one F(9) atom to form VF6 octahedra that share  a cornercorner with one Li(3)F4 tetrahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(2)F4 tetrahedra, and  an edgeedge with one V(3)F5 trigonal bipyramid. In the third V site, V(3) is bonded to one F(10), one F(11), one F(4), one F(5), and one F(7) atom to form VF5 trigonal bipyramids that share  a cornercorner with one Li(2)F4 tetrahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra,  an edgeedge with one V(1)F6 octahedra, and  an edgeedge with one V(2)F6 octahedra. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(1) 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(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(2) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(3) atom. In the sixth F site, F(6) is bonded in a linear geometry to one Li(3) and one V(2) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one Li(3) and one V(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Li(1) and one V(2) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one Li(2) and one V(2) 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(3) atom. In the eleventh F site, F(11) is bonded in a trigonal planar geometry to one Li(3), one V(1), and one V(3) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one Li(3) and one V(1) atom.
LiVF4 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(4), one F(5), and one F(8) atom to form LiF4 tetrahedra that share corners with two equivalent V(1)F6 octahedra, corners with two equivalent V(2)F6 octahedra, and corners with two equivalent V(3)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 20-63°. The Li(1)-F(1) bond length is 1.89 Å. The Li(1)-F(4) bond length is 2.00 Å. The Li(1)-F(5) bond length is 1.97 Å. The Li(1)-F(8) bond length is 1.81 Å. In the second Li site, Li(2) is bonded to one F(10), one F(2), one F(3), and one F(9) atom to form LiF4 tetrahedra that share corners with two equivalent V(1)F6 octahedra, corners with three equivalent V(2)F6 octahedra, and  a cornercorner with one V(3)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 36-55°. The Li(2)-F(10) bond length is 2.00 Å. The Li(2)-F(2) bond length is 1.81 Å. The Li(2)-F(3) bond length is 2.07 Å. The Li(2)-F(9) bond length is 1.80 Å. In the third Li site, Li(3) is bonded to one F(11), one F(12), one F(6), and one F(7) atom to form LiF4 tetrahedra that share  a cornercorner with one V(2)F6 octahedra, corners with two equivalent V(1)F6 octahedra, and corners with two equivalent V(3)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 13-56°. The Li(3)-F(11) bond length is 2.19 Å. The Li(3)-F(12) bond length is 1.89 Å. The Li(3)-F(6) bond length is 1.82 Å. The Li(3)-F(7) bond length is 1.93 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one F(1), one F(11), one F(12), one F(4), and two equivalent F(3) atoms to form VF6 octahedra that share corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(2)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra,  an edgeedge with one V(1)F6 octahedra, and  an edgeedge with one V(3)F5 trigonal bipyramid. The V(1)-F(1) bond length is 1.88 Å. The V(1)-F(11) bond length is 2.14 Å. The V(1)-F(12) bond length is 1.88 Å. The V(1)-F(4) bond length is 2.01 Å. There is one shorter (2.04 Å) and one longer (2.08 Å) V(1)-F(3) bond length. In the second V site, V(2) is bonded to one F(10), one F(2), one F(5), one F(6), one F(8), and one F(9) atom to form VF6 octahedra that share  a cornercorner with one Li(3)F4 tetrahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(2)F4 tetrahedra, and  an edgeedge with one V(3)F5 trigonal bipyramid. The V(2)-F(10) bond length is 2.22 Å. The V(2)-F(2) bond length is 1.91 Å. The V(2)-F(5) bond length is 2.16 Å. The V(2)-F(6) bond length is 1.93 Å. The V(2)-F(8) bond length is 1.92 Å. The V(2)-F(9) bond length is 1.91 Å. In the third V site, V(3) is bonded to one F(10), one F(11), one F(4), one F(5), and one F(7) atom to form VF5 trigonal bipyramids that share  a cornercorner with one Li(2)F4 tetrahedra, corners with two equivalent Li(1)F4 tetrahedra, corners with two equivalent Li(3)F4 tetrahedra,  an edgeedge with one V(1)F6 octahedra, and  an edgeedge with one V(2)F6 octahedra. The V(3)-F(10) bond length is 1.91 Å. The V(3)-F(11) bond length is 1.94 Å. The V(3)-F(4) bond length is 2.07 Å. The V(3)-F(5) bond length is 1.95 Å. The V(3)-F(7) bond length is 1.84 Å. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(1) 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(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(2) and two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(3) atom. In the sixth F site, F(6) is bonded in a linear geometry to one Li(3) and one V(2) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one Li(3) and one V(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Li(1) and one V(2) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one Li(2) and one V(2) 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(3) atom. In the eleventh F site, F(11) is bonded in a trigonal planar geometry to one Li(3), one V(1), and one V(3) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one Li(3) and one V(1) atom.