LiV3OF11 crystallizes in the triclinic P1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(13), one F(15), one F(17), one F(21), one F(6), and one F(7) atom to form LiF6 octahedra that share  a cornercorner with one V(1)OF5 octahedra,  a cornercorner with one V(3)OF5 octahedra,  a cornercorner with one V(4)OF5 octahedra, and  a cornercorner with one V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-40°. In the second Li site, Li(2) is bonded to one F(14), one F(16), one F(18), one F(22), one F(5), and one F(8) atom to form LiF6 octahedra that share  a cornercorner with one V(1)OF5 octahedra,  a cornercorner with one V(3)OF5 octahedra,  a cornercorner with one V(4)OF5 octahedra, and  a cornercorner with one V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-40°. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one F(10), one F(12), one F(14), one F(2), and one F(6) atom to form VOF5 octahedra that share  a cornercorner with one Li(1)F6 octahedra,  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one V(3)OF5 octahedra, and  a cornercorner with one V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 1-40°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(2), one F(10), one F(12), one F(15), one F(18), and one F(3) atom. In the third V site, V(3) is bonded to one O(1), one F(2), one F(20), one F(22), one F(4), and one F(7) atom to form VOF5 octahedra that share  a cornercorner with one Li(1)F6 octahedra,  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one V(1)OF5 octahedra, and  a cornercorner with one V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 1-33°. In the fourth V site, V(4) is bonded to one O(1), one F(1), one F(11), one F(13), one F(5), and one F(9) atom to form VOF5 octahedra that share  a cornercorner with one Li(1)F6 octahedra,  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one V(3)OF5 octahedra, and  a cornercorner with one V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 1-40°. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(1), one F(11), one F(16), one F(17), one F(4), and one F(9) atom. In the sixth V site, V(6) is bonded to one O(2), one F(1), one F(19), one F(21), one F(3), and one F(8) atom to form VOF5 octahedra that share  a cornercorner with one Li(1)F6 octahedra,  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one V(1)OF5 octahedra, and  a cornercorner with one V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 1-33°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(3), one V(4), and one V(5) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(2), and one V(6) atom. There are twenty-two inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one V(4) and one V(6) atom. In the second F site, F(2) is bonded in a linear geometry to one V(1) and one V(3) atom. In the third F site, F(3) is bonded in a water-like geometry to one V(2) and one V(6) atom. In the fourth F site, F(4) is bonded in a water-like geometry to one V(3) and one V(5) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(2) and one V(4) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one Li(1) and one V(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Li(2) and one V(6) atom. In the ninth F site, F(9) is bonded in a distorted bent 150 degrees geometry to one V(4) and one V(5) atom. In the tenth F site, F(10) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(2) atom. In the eleventh F site, F(11) is bonded in a water-like geometry to one V(4) and one V(5) atom. In the twelfth F site, F(12) is bonded in a water-like geometry to one V(1) and one V(2) atom. In the thirteenth F site, F(13) is bonded in a bent 150 degrees geometry to one Li(1) and one V(4) atom. In the fourteenth F site, F(14) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the fifteenth F site, F(15) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(2) atom. In the sixteenth F site, F(16) is bonded in a distorted bent 150 degrees geometry to one Li(2) and one V(5) atom. In the seventeenth F site, F(17) is bonded in a bent 150 degrees geometry to one Li(1) and one V(5) atom. In the eighteenth F site, F(18) is bonded in a bent 150 degrees geometry to one Li(2) and one V(2) atom. In the nineteenth F site, F(19) is bonded in a single-bond geometry to one V(6) atom. In the twentieth F site, F(20) is bonded in a single-bond geometry to one V(3) atom. In the twenty-first F site, F(21) is bonded in a bent 150 degrees geometry to one Li(1) and one V(6) atom. In the twenty-second F site, F(22) is bonded in a bent 150 degrees geometry to one Li(2) and one V(3) atom.
LiV3OF11 crystallizes in the triclinic P1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(13), one F(15), one F(17), one F(21), one F(6), and one F(7) atom to form LiF6 octahedra that share  a cornercorner with one V(1)OF5 octahedra,  a cornercorner with one V(3)OF5 octahedra,  a cornercorner with one V(4)OF5 octahedra, and  a cornercorner with one V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-40°. The Li(1)-F(13) bond length is 1.97 Å. The Li(1)-F(15) bond length is 2.28 Å. The Li(1)-F(17) bond length is 2.28 Å. The Li(1)-F(21) bond length is 1.93 Å. The Li(1)-F(6) bond length is 2.28 Å. The Li(1)-F(7) bond length is 2.01 Å. In the second Li site, Li(2) is bonded to one F(14), one F(16), one F(18), one F(22), one F(5), and one F(8) atom to form LiF6 octahedra that share  a cornercorner with one V(1)OF5 octahedra,  a cornercorner with one V(3)OF5 octahedra,  a cornercorner with one V(4)OF5 octahedra, and  a cornercorner with one V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-40°. The Li(2)-F(14) bond length is 1.97 Å. The Li(2)-F(16) bond length is 2.28 Å. The Li(2)-F(18) bond length is 2.28 Å. The Li(2)-F(22) bond length is 1.93 Å. The Li(2)-F(5) bond length is 2.27 Å. The Li(2)-F(8) bond length is 2.02 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one F(10), one F(12), one F(14), one F(2), and one F(6) atom to form VOF5 octahedra that share  a cornercorner with one Li(1)F6 octahedra,  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one V(3)OF5 octahedra, and  a cornercorner with one V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 1-40°. The V(1)-O(2) bond length is 1.93 Å. The V(1)-F(10) bond length is 1.87 Å. The V(1)-F(12) bond length is 2.04 Å. The V(1)-F(14) bond length is 1.85 Å. The V(1)-F(2) bond length is 1.99 Å. The V(1)-F(6) bond length is 1.79 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(2), one F(10), one F(12), one F(15), one F(18), and one F(3) atom. The V(2)-O(2) bond length is 1.87 Å. The V(2)-F(10) bond length is 2.17 Å. The V(2)-F(12) bond length is 1.94 Å. The V(2)-F(15) bond length is 1.79 Å. The V(2)-F(18) bond length is 1.80 Å. The V(2)-F(3) bond length is 1.99 Å. In the third V site, V(3) is bonded to one O(1), one F(2), one F(20), one F(22), one F(4), and one F(7) atom to form VOF5 octahedra that share  a cornercorner with one Li(1)F6 octahedra,  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one V(1)OF5 octahedra, and  a cornercorner with one V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 1-33°. The V(3)-O(1) bond length is 2.07 Å. The V(3)-F(2) bond length is 1.99 Å. The V(3)-F(20) bond length is 1.76 Å. The V(3)-F(22) bond length is 1.84 Å. The V(3)-F(4) bond length is 2.00 Å. The V(3)-F(7) bond length is 1.81 Å. In the fourth V site, V(4) is bonded to one O(1), one F(1), one F(11), one F(13), one F(5), and one F(9) atom to form VOF5 octahedra that share  a cornercorner with one Li(1)F6 octahedra,  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one V(3)OF5 octahedra, and  a cornercorner with one V(6)OF5 octahedra. The corner-sharing octahedral tilt angles range from 1-40°. The V(4)-O(1) bond length is 1.93 Å. The V(4)-F(1) bond length is 1.99 Å. The V(4)-F(11) bond length is 2.04 Å. The V(4)-F(13) bond length is 1.85 Å. The V(4)-F(5) bond length is 1.79 Å. The V(4)-F(9) bond length is 1.87 Å. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(1), one F(11), one F(16), one F(17), one F(4), and one F(9) atom. The V(5)-O(1) bond length is 1.87 Å. The V(5)-F(11) bond length is 1.95 Å. The V(5)-F(16) bond length is 1.79 Å. The V(5)-F(17) bond length is 1.80 Å. The V(5)-F(4) bond length is 1.99 Å. The V(5)-F(9) bond length is 2.17 Å. In the sixth V site, V(6) is bonded to one O(2), one F(1), one F(19), one F(21), one F(3), and one F(8) atom to form VOF5 octahedra that share  a cornercorner with one Li(1)F6 octahedra,  a cornercorner with one Li(2)F6 octahedra,  a cornercorner with one V(1)OF5 octahedra, and  a cornercorner with one V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 1-33°. The V(6)-O(2) bond length is 2.06 Å. The V(6)-F(1) bond length is 1.99 Å. The V(6)-F(19) bond length is 1.76 Å. The V(6)-F(21) bond length is 1.84 Å. The V(6)-F(3) bond length is 2.00 Å. The V(6)-F(8) bond length is 1.81 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(3), one V(4), and one V(5) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(2), and one V(6) atom. There are twenty-two inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one V(4) and one V(6) atom. In the second F site, F(2) is bonded in a linear geometry to one V(1) and one V(3) atom. In the third F site, F(3) is bonded in a water-like geometry to one V(2) and one V(6) atom. In the fourth F site, F(4) is bonded in a water-like geometry to one V(3) and one V(5) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one Li(2) and one V(4) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one Li(1) and one V(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one Li(2) and one V(6) atom. In the ninth F site, F(9) is bonded in a distorted bent 150 degrees geometry to one V(4) and one V(5) atom. In the tenth F site, F(10) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(2) atom. In the eleventh F site, F(11) is bonded in a water-like geometry to one V(4) and one V(5) atom. In the twelfth F site, F(12) is bonded in a water-like geometry to one V(1) and one V(2) atom. In the thirteenth F site, F(13) is bonded in a bent 150 degrees geometry to one Li(1) and one V(4) atom. In the fourteenth F site, F(14) is bonded in a bent 150 degrees geometry to one Li(2) and one V(1) atom. In the fifteenth F site, F(15) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(2) atom. In the sixteenth F site, F(16) is bonded in a distorted bent 150 degrees geometry to one Li(2) and one V(5) atom. In the seventeenth F site, F(17) is bonded in a bent 150 degrees geometry to one Li(1) and one V(5) atom. In the eighteenth F site, F(18) is bonded in a bent 150 degrees geometry to one Li(2) and one V(2) atom. In the nineteenth F site, F(19) is bonded in a single-bond geometry to one V(6) atom. In the twentieth F site, F(20) is bonded in a single-bond geometry to one V(3) atom. In the twenty-first F site, F(21) is bonded in a bent 150 degrees geometry to one Li(1) and one V(6) atom. In the twenty-second F site, F(22) is bonded in a bent 150 degrees geometry to one Li(2) and one V(3) atom.