LiVF4 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(10), one F(7), and one F(9) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(6)F6 octahedra, and  an edgeedge with one Li(3)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-71°. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(14), one F(15), one F(6), one F(7), and one F(9) atom. In the third Li site, Li(3) is bonded to one F(10), one F(13), one F(18), and one F(9) atom to form LiF4 tetrahedra that share  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(6)F6 octahedra,  a cornercorner with one Li(5)F4 trigonal pyramid, and  an edgeedge with one Li(1)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 27-68°. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one F(12), one F(15), one F(16), one F(7), and one F(8) atom. In the fifth Li site, Li(5) is bonded to one F(15), one F(16), one F(18), and one F(24) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(5)F6 octahedra,  a cornercorner with one V(6)F6 octahedra, and  a cornercorner with one Li(3)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 19-72°. In the sixth Li site, Li(6) is bonded to one F(19), one F(20), one F(23), and one F(3) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  an edgeedge with one V(2)F6 octahedra, and  an edgeedge with one V(5)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-65°. There are six inequivalent V sites. In the first V site, V(1) is bonded to one F(21), one F(24), one F(3), one F(4), one F(7), and one F(8) atom to form VF6 octahedra that share  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one Li(1)F4 trigonal pyramid,  a cornercorner with one Li(5)F4 trigonal pyramid,  a cornercorner with one Li(6)F4 trigonal pyramid, and  an edgeedge with one V(6)F6 octahedra. The corner-sharing octahedral tilt angles range from 30-37°. In the second V site, V(2) is bonded to one F(10), one F(11), one F(2), one F(23), one F(3), and one F(6) atom to form VF6 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one Li(3)F4 tetrahedra,  a cornercorner with one Li(1)F4 trigonal pyramid,  an edgeedge with one V(5)F6 octahedra, and  an edgeedge with one Li(6)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 31-37°. In the third V site, V(3) is bonded to one F(12), one F(14), one F(17), one F(20), one F(5), and one F(9) atom to form VF6 octahedra that share  a cornercorner with one V(5)F6 octahedra,  a cornercorner with one V(6)F6 octahedra,  a cornercorner with one Li(3)F4 tetrahedra,  a cornercorner with one Li(1)F4 trigonal pyramid,  a cornercorner with one Li(6)F4 trigonal pyramid, and  an edgeedge with one V(4)F6 octahedra. The corner-sharing octahedral tilt angles are 31°. In the fourth V site, V(4) is bonded to one F(11), one F(13), one F(16), one F(20), one F(5), and one F(8) atom to form VF6 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one Li(3)F4 tetrahedra,  a cornercorner with one Li(5)F4 trigonal pyramid,  a cornercorner with one Li(6)F4 trigonal pyramid, and  an edgeedge with one V(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 30-31°. In the fifth V site, V(5) is bonded to one F(14), one F(15), one F(19), one F(2), one F(22), and one F(23) atom to form VF6 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(6)F6 octahedra,  a cornercorner with one Li(5)F4 trigonal pyramid,  an edgeedge with one V(2)F6 octahedra, and  an edgeedge with one Li(6)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 31-32°. In the sixth V site, V(6) is bonded to one F(1), one F(17), one F(18), one F(21), one F(22), and one F(4) atom to form VF6 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(5)F6 octahedra,  a cornercorner with one Li(3)F4 tetrahedra,  a cornercorner with one Li(1)F4 trigonal pyramid,  a cornercorner with one Li(5)F4 trigonal pyramid, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 31-32°. There are twenty-four 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(6) atom. In the second F site, F(2) is bonded in a water-like geometry to one V(2) and one V(5) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(6), one V(1), and one V(2) atom. In the fourth F site, F(4) is bonded in a water-like geometry to one V(1) and one V(6) atom. In the fifth F site, F(5) is bonded in a water-like geometry to one V(3) and one V(4) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Li(2) and one V(2) atom. In the seventh F site, F(7) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one V(1) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Li(4), one V(1), and one V(4) atom. In the ninth F site, F(9) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(3) atom. In the tenth F site, F(10) is bonded in a distorted T-shaped geometry to one Li(1), one Li(3), and one V(2) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one Li(4) and one V(3) atom. In the thirteenth F site, F(13) is bonded in a bent 150 degrees geometry to one Li(3) and one V(4) atom. In the fourteenth F site, F(14) is bonded in a distorted T-shaped geometry to one Li(2), one V(3), and one V(5) atom. In the fifteenth F site, F(15) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(4), one Li(5), and one V(5) atom. In the sixteenth F site, F(16) is bonded in a T-shaped geometry to one Li(4), one Li(5), and one V(4) atom. In the seventeenth F site, F(17) is bonded in a bent 150 degrees geometry to one V(3) and one V(6) atom. In the eighteenth F site, F(18) is bonded in a trigonal planar geometry to one Li(3), one Li(5), and one V(6) atom. In the nineteenth F site, F(19) is bonded in a water-like geometry to one Li(6) and one V(5) atom. In the twentieth F site, F(20) is bonded in a distorted trigonal planar geometry to one Li(6), one V(3), and one V(4) atom. In the twenty-first F site, F(21) is bonded in a water-like geometry to one V(1) and one V(6) atom. In the twenty-second F site, F(22) is bonded in a bent 150 degrees geometry to one V(5) and one V(6) atom. In the twenty-third F site, F(23) is bonded in a distorted trigonal non-coplanar geometry to one Li(6), one V(2), and one V(5) atom. In the twenty-fourth F site, F(24) is bonded in a bent 150 degrees geometry to one Li(5) and one V(1) atom.
LiVF4 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(10), one F(7), and one F(9) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(6)F6 octahedra, and  an edgeedge with one Li(3)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-71°. The Li(1)-F(1) bond length is 1.79 Å. The Li(1)-F(10) bond length is 1.89 Å. The Li(1)-F(7) bond length is 1.94 Å. The Li(1)-F(9) bond length is 1.96 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(14), one F(15), one F(6), one F(7), and one F(9) atom. The Li(2)-F(14) bond length is 2.48 Å. The Li(2)-F(15) bond length is 1.91 Å. The Li(2)-F(6) bond length is 1.79 Å. The Li(2)-F(7) bond length is 2.08 Å. The Li(2)-F(9) bond length is 1.94 Å. In the third Li site, Li(3) is bonded to one F(10), one F(13), one F(18), and one F(9) atom to form LiF4 tetrahedra that share  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(6)F6 octahedra,  a cornercorner with one Li(5)F4 trigonal pyramid, and  an edgeedge with one Li(1)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 27-68°. The Li(3)-F(10) bond length is 1.91 Å. The Li(3)-F(13) bond length is 1.82 Å. The Li(3)-F(18) bond length is 1.88 Å. The Li(3)-F(9) bond length is 2.05 Å. In the fourth Li site, Li(4) is bonded in a 5-coordinate geometry to one F(12), one F(15), one F(16), one F(7), and one F(8) atom. The Li(4)-F(12) bond length is 1.78 Å. The Li(4)-F(15) bond length is 2.10 Å. The Li(4)-F(16) bond length is 1.87 Å. The Li(4)-F(7) bond length is 1.96 Å. The Li(4)-F(8) bond length is 2.43 Å. In the fifth Li site, Li(5) is bonded to one F(15), one F(16), one F(18), and one F(24) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(5)F6 octahedra,  a cornercorner with one V(6)F6 octahedra, and  a cornercorner with one Li(3)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 19-72°. The Li(5)-F(15) bond length is 2.00 Å. The Li(5)-F(16) bond length is 1.95 Å. The Li(5)-F(18) bond length is 1.89 Å. The Li(5)-F(24) bond length is 1.86 Å. In the sixth Li site, Li(6) is bonded to one F(19), one F(20), one F(23), and one F(3) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  an edgeedge with one V(2)F6 octahedra, and  an edgeedge with one V(5)F6 octahedra. The corner-sharing octahedral tilt angles range from 42-65°. The Li(6)-F(19) bond length is 1.86 Å. The Li(6)-F(20) bond length is 1.84 Å. The Li(6)-F(23) bond length is 2.01 Å. The Li(6)-F(3) bond length is 1.94 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one F(21), one F(24), one F(3), one F(4), one F(7), and one F(8) atom to form VF6 octahedra that share  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one Li(1)F4 trigonal pyramid,  a cornercorner with one Li(5)F4 trigonal pyramid,  a cornercorner with one Li(6)F4 trigonal pyramid, and  an edgeedge with one V(6)F6 octahedra. The corner-sharing octahedral tilt angles range from 30-37°. The V(1)-F(21) bond length is 1.94 Å. The V(1)-F(24) bond length is 1.89 Å. The V(1)-F(3) bond length is 2.11 Å. The V(1)-F(4) bond length is 2.04 Å. The V(1)-F(7) bond length is 2.03 Å. The V(1)-F(8) bond length is 1.98 Å. In the second V site, V(2) is bonded to one F(10), one F(11), one F(2), one F(23), one F(3), and one F(6) atom to form VF6 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one Li(3)F4 tetrahedra,  a cornercorner with one Li(1)F4 trigonal pyramid,  an edgeedge with one V(5)F6 octahedra, and  an edgeedge with one Li(6)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 31-37°. The V(2)-F(10) bond length is 1.93 Å. The V(2)-F(11) bond length is 2.01 Å. The V(2)-F(2) bond length is 2.08 Å. The V(2)-F(23) bond length is 2.00 Å. The V(2)-F(3) bond length is 2.09 Å. The V(2)-F(6) bond length is 1.88 Å. In the third V site, V(3) is bonded to one F(12), one F(14), one F(17), one F(20), one F(5), and one F(9) atom to form VF6 octahedra that share  a cornercorner with one V(5)F6 octahedra,  a cornercorner with one V(6)F6 octahedra,  a cornercorner with one Li(3)F4 tetrahedra,  a cornercorner with one Li(1)F4 trigonal pyramid,  a cornercorner with one Li(6)F4 trigonal pyramid, and  an edgeedge with one V(4)F6 octahedra. The corner-sharing octahedral tilt angles are 31°. The V(3)-F(12) bond length is 1.88 Å. The V(3)-F(14) bond length is 1.97 Å. The V(3)-F(17) bond length is 2.01 Å. The V(3)-F(20) bond length is 2.07 Å. The V(3)-F(5) bond length is 1.99 Å. The V(3)-F(9) bond length is 2.03 Å. In the fourth V site, V(4) is bonded to one F(11), one F(13), one F(16), one F(20), one F(5), and one F(8) atom to form VF6 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one Li(3)F4 tetrahedra,  a cornercorner with one Li(5)F4 trigonal pyramid,  a cornercorner with one Li(6)F4 trigonal pyramid, and  an edgeedge with one V(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 30-31°. The V(4)-F(11) bond length is 1.98 Å. The V(4)-F(13) bond length is 1.88 Å. The V(4)-F(16) bond length is 1.97 Å. The V(4)-F(20) bond length is 2.09 Å. The V(4)-F(5) bond length is 1.99 Å. The V(4)-F(8) bond length is 2.07 Å. In the fifth V site, V(5) is bonded to one F(14), one F(15), one F(19), one F(2), one F(22), and one F(23) atom to form VF6 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(6)F6 octahedra,  a cornercorner with one Li(5)F4 trigonal pyramid,  an edgeedge with one V(2)F6 octahedra, and  an edgeedge with one Li(6)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 31-32°. The V(5)-F(14) bond length is 2.05 Å. The V(5)-F(15) bond length is 2.04 Å. The V(5)-F(19) bond length is 1.88 Å. The V(5)-F(2) bond length is 1.95 Å. The V(5)-F(22) bond length is 1.97 Å. The V(5)-F(23) bond length is 2.11 Å. In the sixth V site, V(6) is bonded to one F(1), one F(17), one F(18), one F(21), one F(22), and one F(4) atom to form VF6 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(5)F6 octahedra,  a cornercorner with one Li(3)F4 tetrahedra,  a cornercorner with one Li(1)F4 trigonal pyramid,  a cornercorner with one Li(5)F4 trigonal pyramid, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 31-32°. The V(6)-F(1) bond length is 1.87 Å. The V(6)-F(17) bond length is 2.01 Å. The V(6)-F(18) bond length is 1.95 Å. The V(6)-F(21) bond length is 2.09 Å. The V(6)-F(22) bond length is 2.06 Å. The V(6)-F(4) bond length is 1.97 Å. There are twenty-four 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(6) atom. In the second F site, F(2) is bonded in a water-like geometry to one V(2) and one V(5) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(6), one V(1), and one V(2) atom. In the fourth F site, F(4) is bonded in a water-like geometry to one V(1) and one V(6) atom. In the fifth F site, F(5) is bonded in a water-like geometry to one V(3) and one V(4) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Li(2) and one V(2) atom. In the seventh F site, F(7) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one V(1) atom. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Li(4), one V(1), and one V(4) atom. In the ninth F site, F(9) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one V(3) atom. In the tenth F site, F(10) is bonded in a distorted T-shaped geometry to one Li(1), one Li(3), and one V(2) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one Li(4) and one V(3) atom. In the thirteenth F site, F(13) is bonded in a bent 150 degrees geometry to one Li(3) and one V(4) atom. In the fourteenth F site, F(14) is bonded in a distorted T-shaped geometry to one Li(2), one V(3), and one V(5) atom. In the fifteenth F site, F(15) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(4), one Li(5), and one V(5) atom. In the sixteenth F site, F(16) is bonded in a T-shaped geometry to one Li(4), one Li(5), and one V(4) atom. In the seventeenth F site, F(17) is bonded in a bent 150 degrees geometry to one V(3) and one V(6) atom. In the eighteenth F site, F(18) is bonded in a trigonal planar geometry to one Li(3), one Li(5), and one V(6) atom. In the nineteenth F site, F(19) is bonded in a water-like geometry to one Li(6) and one V(5) atom. In the twentieth F site, F(20) is bonded in a distorted trigonal planar geometry to one Li(6), one V(3), and one V(4) atom. In the twenty-first F site, F(21) is bonded in a water-like geometry to one V(1) and one V(6) atom. In the twenty-second F site, F(22) is bonded in a bent 150 degrees geometry to one V(5) and one V(6) atom. In the twenty-third F site, F(23) is bonded in a distorted trigonal non-coplanar geometry to one Li(6), one V(2), and one V(5) atom. In the twenty-fourth F site, F(24) is bonded in a bent 150 degrees geometry to one Li(5) and one V(1) atom.