LiVF4 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(3), one F(4), one F(7), and two equivalent F(5) atoms. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(1), one F(5), one F(6), and two equivalent F(7) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one F(2), one F(3), one F(7), one F(9), and two equivalent F(1) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the second V site, V(2) is bonded to one F(2), one F(5), one F(6), one F(8), and two equivalent F(4) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(2) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Li(1) and two equivalent V(2) atoms. In the fifth F site, F(5) is bonded to one Li(2), two equivalent Li(1), and one V(2) atom to form a mixture of corner and edge-sharing FLi3V trigonal pyramids. In the sixth F site, F(6) is bonded in a water-like geometry to one Li(2) and one V(2) atom. In the seventh F site, F(7) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form a mixture of corner and edge-sharing FLi3V tetrahedra. In the eighth F site, F(8) is bonded in a linear geometry to two equivalent V(2) atoms. In the ninth F site, F(9) is bonded in a linear geometry to two equivalent V(1) atoms.
LiVF4 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(3), one F(4), one F(7), and two equivalent F(5) atoms. The Li(1)-F(3) bond length is 1.88 Å. The Li(1)-F(4) bond length is 2.25 Å. The Li(1)-F(7) bond length is 2.17 Å. Both Li(1)-F(5) bond lengths are 2.05 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(1), one F(5), one F(6), and two equivalent F(7) atoms. The Li(2)-F(1) bond length is 2.48 Å. The Li(2)-F(5) bond length is 2.06 Å. The Li(2)-F(6) bond length is 1.95 Å. Both Li(2)-F(7) bond lengths are 2.12 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one F(2), one F(3), one F(7), one F(9), and two equivalent F(1) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 0-13°. The V(1)-F(2) bond length is 1.98 Å. The V(1)-F(3) bond length is 1.87 Å. The V(1)-F(7) bond length is 2.02 Å. The V(1)-F(9) bond length is 2.00 Å. Both V(1)-F(1) bond lengths are 2.00 Å. In the second V site, V(2) is bonded to one F(2), one F(5), one F(6), one F(8), and two equivalent F(4) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. The V(2)-F(2) bond length is 1.98 Å. The V(2)-F(5) bond length is 1.97 Å. The V(2)-F(6) bond length is 1.90 Å. The V(2)-F(8) bond length is 1.96 Å. Both V(2)-F(4) bond lengths are 1.99 Å. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(2) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Li(1) and two equivalent V(2) atoms. In the fifth F site, F(5) is bonded to one Li(2), two equivalent Li(1), and one V(2) atom to form a mixture of corner and edge-sharing FLi3V trigonal pyramids. In the sixth F site, F(6) is bonded in a water-like geometry to one Li(2) and one V(2) atom. In the seventh F site, F(7) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form a mixture of corner and edge-sharing FLi3V tetrahedra. In the eighth F site, F(8) is bonded in a linear geometry to two equivalent V(2) atoms. In the ninth F site, F(9) is bonded in a linear geometry to two equivalent V(1) atoms.