LiNbVO4 is Spinel-derived structured and crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), one O(6), and one O(8) atom to form LiO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Nb(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, and corners with three equivalent Nb(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one Nb(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and corners with three equivalent Nb(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-61°. There are three inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(7) atoms to form NbO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent Nb(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. In the second Nb site, Nb(2) is bonded to two equivalent O(2), two equivalent O(6), and two equivalent O(8) atoms to form NbO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, edges with two equivalent Nb(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. In the third Nb site, Nb(3) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form NbO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra,  an edgeedge with one Nb(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and  an edgeedge with one V(4)O6 octahedra. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, edges with two equivalent Nb(2)O6 octahedra, edges with two equivalent Nb(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent Nb(3)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent Nb(3)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. In the fourth V site, V(4) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, edges with two equivalent Nb(2)O6 octahedra, edges with two equivalent Nb(3)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Nb(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Nb(2), one V(1), and one V(4) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Nb(3), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Nb(3), one V(1), and one V(4) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(2), one Nb(1), one Nb(3), and one V(3) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Nb(2), one Nb(3), and one V(1) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), one Nb(1), one Nb(3), and one V(2) atom. In the eighth O site, O(8) is bonded to one Li(1), one Nb(2), one Nb(3), and one V(4) atom to form distorted corner-sharing OLiNb2V trigonal pyramids.
LiNbVO4 is Spinel-derived structured and crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), one O(6), and one O(8) atom to form LiO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Nb(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, and corners with three equivalent Nb(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. The Li(1)-O(1) bond length is 2.01 Å. The Li(1)-O(4) bond length is 2.05 Å. The Li(1)-O(6) bond length is 2.07 Å. The Li(1)-O(8) bond length is 2.05 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one Nb(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and corners with three equivalent Nb(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-61°. The Li(2)-O(2) bond length is 2.04 Å. The Li(2)-O(3) bond length is 2.01 Å. The Li(2)-O(5) bond length is 2.07 Å. The Li(2)-O(7) bond length is 2.05 Å. There are three inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(7) atoms to form NbO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent Nb(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. Both Nb(1)-O(1) bond lengths are 2.00 Å. Both Nb(1)-O(5) bond lengths are 2.08 Å. Both Nb(1)-O(7) bond lengths are 2.06 Å. In the second Nb site, Nb(2) is bonded to two equivalent O(2), two equivalent O(6), and two equivalent O(8) atoms to form NbO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, edges with two equivalent Nb(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. Both Nb(2)-O(2) bond lengths are 2.01 Å. Both Nb(2)-O(6) bond lengths are 2.11 Å. Both Nb(2)-O(8) bond lengths are 2.11 Å. In the third Nb site, Nb(3) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form NbO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra,  an edgeedge with one Nb(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and  an edgeedge with one V(4)O6 octahedra. The Nb(3)-O(3) bond length is 1.97 Å. The Nb(3)-O(4) bond length is 2.05 Å. The Nb(3)-O(5) bond length is 2.08 Å. The Nb(3)-O(6) bond length is 2.09 Å. The Nb(3)-O(7) bond length is 2.10 Å. The Nb(3)-O(8) bond length is 2.06 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, edges with two equivalent Nb(2)O6 octahedra, edges with two equivalent Nb(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. Both V(1)-O(2) bond lengths are 2.08 Å. Both V(1)-O(4) bond lengths are 2.04 Å. Both V(1)-O(6) bond lengths are 2.10 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent Nb(3)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. Both V(2)-O(1) bond lengths are 2.13 Å. Both V(2)-O(3) bond lengths are 2.14 Å. Both V(2)-O(7) bond lengths are 2.14 Å. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent Nb(3)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. Both V(3)-O(1) bond lengths are 2.13 Å. Both V(3)-O(3) bond lengths are 2.15 Å. Both V(3)-O(5) bond lengths are 2.15 Å. In the fourth V site, V(4) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, edges with two equivalent Nb(2)O6 octahedra, edges with two equivalent Nb(3)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. Both V(4)-O(2) bond lengths are 2.14 Å. Both V(4)-O(4) bond lengths are 2.13 Å. Both V(4)-O(8) bond lengths are 2.12 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Nb(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Nb(2), one V(1), and one V(4) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Nb(3), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Nb(3), one V(1), and one V(4) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(2), one Nb(1), one Nb(3), and one V(3) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Nb(2), one Nb(3), and one V(1) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), one Nb(1), one Nb(3), and one V(2) atom. In the eighth O site, O(8) is bonded to one Li(1), one Nb(2), one Nb(3), and one V(4) atom to form distorted corner-sharing OLiNb2V trigonal pyramids.