LiVF4 crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(10), one F(12), one F(3), one F(6), and one F(8) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one F(11), one F(12), one F(16), and one F(8) atom. In the third Li site, Li(3) is bonded to one F(13), one F(14), one F(17), and one F(9) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(5)F6 octahedra, and corners with two equivalent V(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 14-71°. In the fourth Li site, Li(4) is bonded to one F(16), one F(19), one F(20), and one F(24) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(6)F6 octahedra,  a cornercorner with one V(7)F6 octahedra, and corners with two equivalent V(5)F6 octahedra. The corner-sharing octahedral tilt angles range from 25-67°. In the fifth Li site, Li(5) is bonded in a 3-coordinate geometry to one F(17), one F(18), one F(21), one F(22), and one F(25) atom. In the sixth Li site, Li(6) is bonded in a rectangular see-saw-like geometry to one F(24), one F(27), one F(28), and one F(32) atom. In the seventh Li site, Li(7) is bonded to one F(1), one F(25), one F(29), and one F(30) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(6)F6 octahedra,  a cornercorner with one V(7)F6 octahedra, and corners with two equivalent V(8)F6 octahedra. The corner-sharing octahedral tilt angles range from 30-69°. In the eighth Li site, Li(8) is bonded in a distorted rectangular see-saw-like geometry to one F(2), one F(27), one F(30), and one F(4) atom. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one F(30), one F(31), one F(32), one F(4), one F(5), and one F(7) atom to form distorted VF6 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(7)F6 octahedra, corners with two equivalent V(2)F6 octahedra, and  a cornercorner with one Li(7)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-49°. In the second V site, V(2) is bonded to one F(10), one F(11), one F(2), one F(4), one F(5), and one F(9) atom to form VF6 octahedra that share  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(8)F6 octahedra, corners with two equivalent V(1)F6 octahedra, and  a cornercorner with one Li(3)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 33-49°. In the third V site, V(3) is bonded to one F(12), one F(13), one F(15), one F(6), one F(7), and one F(8) atom to form VF6 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(5)F6 octahedra, corners with two equivalent V(4)F6 octahedra, and  a cornercorner with one Li(3)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 32-56°. In the fourth V site, V(4) is bonded to one F(10), one F(12), one F(13), one F(17), one F(18), and one F(19) atom to form distorted VF6 octahedra that share  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one V(6)F6 octahedra, corners with two equivalent V(3)F6 octahedra,  a cornercorner with one Li(4)F4 trigonal pyramid, and corners with two equivalent Li(3)F4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 34-56°. In the fifth V site, V(5) is bonded to one F(14), one F(15), one F(16), one F(20), one F(21), and one F(23) atom to form distorted VF6 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(7)F6 octahedra, corners with two equivalent V(6)F6 octahedra,  a cornercorner with one Li(3)F4 trigonal pyramid, and corners with two equivalent Li(4)F4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 30-52°. In the sixth V site, V(6) is bonded to one F(18), one F(20), one F(21), one F(25), one F(26), and one F(27) atom to form VF6 octahedra that share  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(8)F6 octahedra, corners with two equivalent V(5)F6 octahedra,  a cornercorner with one Li(7)F4 tetrahedra, and  a cornercorner with one Li(4)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 33-52°. In the seventh V site, V(7) is bonded to one F(22), one F(23), one F(24), one F(28), one F(29), and one F(31) atom to form VF6 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(5)F6 octahedra, corners with two equivalent V(8)F6 octahedra,  a cornercorner with one Li(7)F4 tetrahedra, and  a cornercorner with one Li(4)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 30-50°. In the eighth V site, V(8) is bonded to one F(1), one F(2), one F(26), one F(28), one F(29), and one F(3) atom to form distorted VF6 octahedra that share  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one V(6)F6 octahedra, corners with two equivalent V(7)F6 octahedra, and corners with two equivalent Li(7)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-50°. There are thirty-two inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 120 degrees geometry to one Li(7) and one V(8) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(8), one V(2), and one V(8) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(1) and one V(8) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Li(8), one V(1), and one V(2) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the sixth F site, F(6) is bonded in an L-shaped geometry to one Li(1) and one V(3) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the eighth F site, F(8) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(3) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one Li(3) and one V(2) atom. In the tenth F site, F(10) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one V(4) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one Li(2) and one V(2) atom. In the twelfth F site, F(12) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(3), and one V(4) atom. In the thirteenth F site, F(13) is bonded in a trigonal non-coplanar geometry to one Li(3), one V(3), and one V(4) atom. In the fourteenth F site, F(14) is bonded in a linear geometry to one Li(3) and one V(5) atom. In the fifteenth F site, F(15) is bonded in a distorted bent 150 degrees geometry to one V(3) and one V(5) atom. In the sixteenth F site, F(16) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(4), and one V(5) atom. In the seventeenth F site, F(17) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(5), and one V(4) atom. In the eighteenth F site, F(18) is bonded in a distorted bent 150 degrees geometry to one Li(5), one V(4), and one V(6) atom. In the nineteenth F site, F(19) is bonded in a bent 150 degrees geometry to one Li(4) and one V(4) atom. In the twentieth F site, F(20) is bonded in a trigonal planar geometry to one Li(4), one V(5), and one V(6) atom. In the twenty-first F site, F(21) is bonded in a distorted bent 150 degrees geometry to one Li(5), one V(5), and one V(6) atom. In the twenty-second F site, F(22) is bonded in a bent 150 degrees geometry to one Li(5) and one V(7) atom. In the twenty-third F site, F(23) is bonded in a bent 150 degrees geometry to one V(5) and one V(7) atom. In the twenty-fourth F site, F(24) is bonded in a trigonal planar geometry to one Li(4), one Li(6), and one V(7) atom. In the twenty-fifth F site, F(25) is bonded in a distorted trigonal non-coplanar geometry to one Li(5), one Li(7), and one V(6) atom. In the twenty-sixth F site, F(26) is bonded in a distorted bent 150 degrees geometry to one V(6) and one V(8) atom. In the twenty-seventh F site, F(27) is bonded in a distorted T-shaped geometry to one Li(6), one Li(8), and one V(6) atom. In the twenty-eighth F site, F(28) is bonded in a distorted trigonal planar geometry to one Li(6), one V(7), and one V(8) atom. In the twenty-ninth F site, F(29) is bonded in a trigonal non-coplanar geometry to one Li(7), one V(7), and one V(8) atom. In the thirtieth F site, F(30) is bonded in a T-shaped geometry to one Li(7), one Li(8), and one V(1) atom. In the thirty-first F site, F(31) is bonded in a bent 150 degrees geometry to one V(1) and one V(7) atom. In the thirty-second F site, F(32) is bonded in a bent 150 degrees geometry to one Li(6) and one V(1) atom.
LiVF4 crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one F(10), one F(12), one F(3), one F(6), and one F(8) atom. The Li(1)-F(10) bond length is 2.14 Å. The Li(1)-F(12) bond length is 2.01 Å. The Li(1)-F(3) bond length is 1.84 Å. The Li(1)-F(6) bond length is 2.33 Å. The Li(1)-F(8) bond length is 1.98 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one F(11), one F(12), one F(16), and one F(8) atom. The Li(2)-F(11) bond length is 1.85 Å. The Li(2)-F(12) bond length is 2.30 Å. The Li(2)-F(16) bond length is 1.98 Å. The Li(2)-F(8) bond length is 1.94 Å. In the third Li site, Li(3) is bonded to one F(13), one F(14), one F(17), and one F(9) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(5)F6 octahedra, and corners with two equivalent V(4)F6 octahedra. The corner-sharing octahedral tilt angles range from 14-71°. The Li(3)-F(13) bond length is 2.15 Å. The Li(3)-F(14) bond length is 1.90 Å. The Li(3)-F(17) bond length is 1.98 Å. The Li(3)-F(9) bond length is 1.83 Å. In the fourth Li site, Li(4) is bonded to one F(16), one F(19), one F(20), and one F(24) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(6)F6 octahedra,  a cornercorner with one V(7)F6 octahedra, and corners with two equivalent V(5)F6 octahedra. The corner-sharing octahedral tilt angles range from 25-67°. The Li(4)-F(16) bond length is 1.93 Å. The Li(4)-F(19) bond length is 1.85 Å. The Li(4)-F(20) bond length is 2.04 Å. The Li(4)-F(24) bond length is 1.90 Å. In the fifth Li site, Li(5) is bonded in a 3-coordinate geometry to one F(17), one F(18), one F(21), one F(22), and one F(25) atom. The Li(5)-F(17) bond length is 1.91 Å. The Li(5)-F(18) bond length is 2.51 Å. The Li(5)-F(21) bond length is 2.53 Å. The Li(5)-F(22) bond length is 1.86 Å. The Li(5)-F(25) bond length is 1.92 Å. In the sixth Li site, Li(6) is bonded in a rectangular see-saw-like geometry to one F(24), one F(27), one F(28), and one F(32) atom. The Li(6)-F(24) bond length is 1.92 Å. The Li(6)-F(27) bond length is 2.03 Å. The Li(6)-F(28) bond length is 2.00 Å. The Li(6)-F(32) bond length is 1.85 Å. In the seventh Li site, Li(7) is bonded to one F(1), one F(25), one F(29), and one F(30) atom to form distorted LiF4 tetrahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(6)F6 octahedra,  a cornercorner with one V(7)F6 octahedra, and corners with two equivalent V(8)F6 octahedra. The corner-sharing octahedral tilt angles range from 30-69°. The Li(7)-F(1) bond length is 1.80 Å. The Li(7)-F(25) bond length is 1.94 Å. The Li(7)-F(29) bond length is 2.17 Å. The Li(7)-F(30) bond length is 1.89 Å. In the eighth Li site, Li(8) is bonded in a distorted rectangular see-saw-like geometry to one F(2), one F(27), one F(30), and one F(4) atom. The Li(8)-F(2) bond length is 1.95 Å. The Li(8)-F(27) bond length is 1.88 Å. The Li(8)-F(30) bond length is 1.92 Å. The Li(8)-F(4) bond length is 1.93 Å. There are eight inequivalent V sites. In the first V site, V(1) is bonded to one F(30), one F(31), one F(32), one F(4), one F(5), and one F(7) atom to form distorted VF6 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(7)F6 octahedra, corners with two equivalent V(2)F6 octahedra, and  a cornercorner with one Li(7)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-49°. The V(1)-F(30) bond length is 1.94 Å. The V(1)-F(31) bond length is 2.10 Å. The V(1)-F(32) bond length is 1.87 Å. The V(1)-F(4) bond length is 2.08 Å. The V(1)-F(5) bond length is 2.11 Å. The V(1)-F(7) bond length is 2.00 Å. In the second V site, V(2) is bonded to one F(10), one F(11), one F(2), one F(4), one F(5), and one F(9) atom to form VF6 octahedra that share  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(8)F6 octahedra, corners with two equivalent V(1)F6 octahedra, and  a cornercorner with one Li(3)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 33-49°. The V(2)-F(10) bond length is 2.13 Å. The V(2)-F(11) bond length is 1.89 Å. The V(2)-F(2) bond length is 2.06 Å. The V(2)-F(4) bond length is 2.04 Å. The V(2)-F(5) bond length is 2.00 Å. The V(2)-F(9) bond length is 1.89 Å. In the third V site, V(3) is bonded to one F(12), one F(13), one F(15), one F(6), one F(7), and one F(8) atom to form VF6 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(5)F6 octahedra, corners with two equivalent V(4)F6 octahedra, and  a cornercorner with one Li(3)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 32-56°. The V(3)-F(12) bond length is 2.11 Å. The V(3)-F(13) bond length is 2.03 Å. The V(3)-F(15) bond length is 2.03 Å. The V(3)-F(6) bond length is 1.86 Å. The V(3)-F(7) bond length is 2.00 Å. The V(3)-F(8) bond length is 1.95 Å. In the fourth V site, V(4) is bonded to one F(10), one F(12), one F(13), one F(17), one F(18), and one F(19) atom to form distorted VF6 octahedra that share  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one V(6)F6 octahedra, corners with two equivalent V(3)F6 octahedra,  a cornercorner with one Li(4)F4 trigonal pyramid, and corners with two equivalent Li(3)F4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 34-56°. The V(4)-F(10) bond length is 2.02 Å. The V(4)-F(12) bond length is 2.19 Å. The V(4)-F(13) bond length is 2.06 Å. The V(4)-F(17) bond length is 1.90 Å. The V(4)-F(18) bond length is 2.04 Å. The V(4)-F(19) bond length is 1.87 Å. In the fifth V site, V(5) is bonded to one F(14), one F(15), one F(16), one F(20), one F(21), and one F(23) atom to form distorted VF6 octahedra that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(7)F6 octahedra, corners with two equivalent V(6)F6 octahedra,  a cornercorner with one Li(3)F4 trigonal pyramid, and corners with two equivalent Li(4)F4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 30-52°. The V(5)-F(14) bond length is 1.87 Å. The V(5)-F(15) bond length is 2.03 Å. The V(5)-F(16) bond length is 1.92 Å. The V(5)-F(20) bond length is 2.10 Å. The V(5)-F(21) bond length is 2.15 Å. The V(5)-F(23) bond length is 1.99 Å. In the sixth V site, V(6) is bonded to one F(18), one F(20), one F(21), one F(25), one F(26), and one F(27) atom to form VF6 octahedra that share  a cornercorner with one V(4)F6 octahedra,  a cornercorner with one V(8)F6 octahedra, corners with two equivalent V(5)F6 octahedra,  a cornercorner with one Li(7)F4 tetrahedra, and  a cornercorner with one Li(4)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 33-52°. The V(6)-F(18) bond length is 2.01 Å. The V(6)-F(20) bond length is 2.01 Å. The V(6)-F(21) bond length is 1.99 Å. The V(6)-F(25) bond length is 1.96 Å. The V(6)-F(26) bond length is 2.02 Å. The V(6)-F(27) bond length is 1.95 Å. In the seventh V site, V(7) is bonded to one F(22), one F(23), one F(24), one F(28), one F(29), and one F(31) atom to form VF6 octahedra that share  a cornercorner with one V(1)F6 octahedra,  a cornercorner with one V(5)F6 octahedra, corners with two equivalent V(8)F6 octahedra,  a cornercorner with one Li(7)F4 tetrahedra, and  a cornercorner with one Li(4)F4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 30-50°. The V(7)-F(22) bond length is 1.90 Å. The V(7)-F(23) bond length is 2.02 Å. The V(7)-F(24) bond length is 1.95 Å. The V(7)-F(28) bond length is 2.06 Å. The V(7)-F(29) bond length is 2.02 Å. The V(7)-F(31) bond length is 2.01 Å. In the eighth V site, V(8) is bonded to one F(1), one F(2), one F(26), one F(28), one F(29), and one F(3) atom to form distorted VF6 octahedra that share  a cornercorner with one V(2)F6 octahedra,  a cornercorner with one V(6)F6 octahedra, corners with two equivalent V(7)F6 octahedra, and corners with two equivalent Li(7)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-50°. The V(8)-F(1) bond length is 1.86 Å. The V(8)-F(2) bond length is 2.06 Å. The V(8)-F(26) bond length is 2.05 Å. The V(8)-F(28) bond length is 2.15 Å. The V(8)-F(29) bond length is 2.04 Å. The V(8)-F(3) bond length is 1.87 Å. There are thirty-two inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 120 degrees geometry to one Li(7) and one V(8) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(8), one V(2), and one V(8) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one Li(1) and one V(8) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Li(8), one V(1), and one V(2) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the sixth F site, F(6) is bonded in an L-shaped geometry to one Li(1) and one V(3) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the eighth F site, F(8) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(2), and one V(3) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one Li(3) and one V(2) atom. In the tenth F site, F(10) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one V(4) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one Li(2) and one V(2) atom. In the twelfth F site, F(12) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(3), and one V(4) atom. In the thirteenth F site, F(13) is bonded in a trigonal non-coplanar geometry to one Li(3), one V(3), and one V(4) atom. In the fourteenth F site, F(14) is bonded in a linear geometry to one Li(3) and one V(5) atom. In the fifteenth F site, F(15) is bonded in a distorted bent 150 degrees geometry to one V(3) and one V(5) atom. In the sixteenth F site, F(16) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(4), and one V(5) atom. In the seventeenth F site, F(17) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(5), and one V(4) atom. In the eighteenth F site, F(18) is bonded in a distorted bent 150 degrees geometry to one Li(5), one V(4), and one V(6) atom. In the nineteenth F site, F(19) is bonded in a bent 150 degrees geometry to one Li(4) and one V(4) atom. In the twentieth F site, F(20) is bonded in a trigonal planar geometry to one Li(4), one V(5), and one V(6) atom. In the twenty-first F site, F(21) is bonded in a distorted bent 150 degrees geometry to one Li(5), one V(5), and one V(6) atom. In the twenty-second F site, F(22) is bonded in a bent 150 degrees geometry to one Li(5) and one V(7) atom. In the twenty-third F site, F(23) is bonded in a bent 150 degrees geometry to one V(5) and one V(7) atom. In the twenty-fourth F site, F(24) is bonded in a trigonal planar geometry to one Li(4), one Li(6), and one V(7) atom. In the twenty-fifth F site, F(25) is bonded in a distorted trigonal non-coplanar geometry to one Li(5), one Li(7), and one V(6) atom. In the twenty-sixth F site, F(26) is bonded in a distorted bent 150 degrees geometry to one V(6) and one V(8) atom. In the twenty-seventh F site, F(27) is bonded in a distorted T-shaped geometry to one Li(6), one Li(8), and one V(6) atom. In the twenty-eighth F site, F(28) is bonded in a distorted trigonal planar geometry to one Li(6), one V(7), and one V(8) atom. In the twenty-ninth F site, F(29) is bonded in a trigonal non-coplanar geometry to one Li(7), one V(7), and one V(8) atom. In the thirtieth F site, F(30) is bonded in a T-shaped geometry to one Li(7), one Li(8), and one V(1) atom. In the thirty-first F site, F(31) is bonded in a bent 150 degrees geometry to one V(1) and one V(7) atom. In the thirty-second F site, F(32) is bonded in a bent 150 degrees geometry to one Li(6) and one V(1) atom.