LiVF4 crystallizes in the orthorhombic Pmn2_1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(1), two equivalent F(6), and two equivalent F(7) atoms. In the second Li site, Li(2) is bonded in a trigonal non-coplanar geometry to one F(2) and two equivalent F(8) atoms. In the third Li site, Li(3) is bonded in a distorted trigonal planar geometry to one F(3) and two equivalent F(7) atoms. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one F(4) and two equivalent F(5) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one F(2), one F(4), one F(6), one F(7), and two equivalent F(10) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 28-50°. In the second V site, V(2) is bonded to one F(1), one F(3), one F(5), one F(8), and two equivalent F(9) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 26-49°. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a trigonal non-coplanar geometry to one Li(1) and two equivalent V(2) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(2) and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(3) and two equivalent V(2) atoms. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Li(4) and two equivalent V(1) atoms. In the fifth F site, F(5) is bonded in a bent 120 degrees geometry to one Li(4) and one V(2) atom. In the sixth F site, F(6) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(1) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), and one V(1) atom. In the eighth F site, F(8) is bonded in a bent 120 degrees geometry to one Li(2) and one V(2) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms.
LiVF4 crystallizes in the orthorhombic Pmn2_1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(1), two equivalent F(6), and two equivalent F(7) atoms. The Li(1)-F(1) bond length is 2.13 Å. Both Li(1)-F(6) bond lengths are 2.01 Å. Both Li(1)-F(7) bond lengths are 2.36 Å. In the second Li site, Li(2) is bonded in a trigonal non-coplanar geometry to one F(2) and two equivalent F(8) atoms. The Li(2)-F(2) bond length is 2.00 Å. Both Li(2)-F(8) bond lengths are 1.94 Å. In the third Li site, Li(3) is bonded in a distorted trigonal planar geometry to one F(3) and two equivalent F(7) atoms. The Li(3)-F(3) bond length is 1.98 Å. Both Li(3)-F(7) bond lengths are 1.98 Å. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one F(4) and two equivalent F(5) atoms. The Li(4)-F(4) bond length is 2.08 Å. Both Li(4)-F(5) bond lengths are 1.97 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one F(2), one F(4), one F(6), one F(7), and two equivalent F(10) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 28-50°. The V(1)-F(2) bond length is 2.08 Å. The V(1)-F(4) bond length is 2.06 Å. The V(1)-F(6) bond length is 1.88 Å. The V(1)-F(7) bond length is 1.93 Å. There is one shorter (1.97 Å) and one longer (2.00 Å) V(1)-F(10) bond length. In the second V site, V(2) is bonded to one F(1), one F(3), one F(5), one F(8), and two equivalent F(9) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 26-49°. The V(2)-F(1) bond length is 2.07 Å. The V(2)-F(3) bond length is 2.08 Å. The V(2)-F(5) bond length is 1.90 Å. The V(2)-F(8) bond length is 1.90 Å. There is one shorter (1.96 Å) and one longer (1.99 Å) V(2)-F(9) bond length. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a trigonal non-coplanar geometry to one Li(1) and two equivalent V(2) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(2) and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(3) and two equivalent V(2) atoms. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Li(4) and two equivalent V(1) atoms. In the fifth F site, F(5) is bonded in a bent 120 degrees geometry to one Li(4) and one V(2) atom. In the sixth F site, F(6) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(1) atom. In the seventh F site, F(7) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), and one V(1) atom. In the eighth F site, F(8) is bonded in a bent 120 degrees geometry to one Li(2) and one V(2) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms.