Li4NbV3O8 is alpha Po-derived structured and crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Nb(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. In the fourth Li site, Li(4) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. Nb(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form NbO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Li(4), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with six equivalent O(1)Li3V3 octahedra, edges with four equivalent O(2)Li3NbV2 octahedra, edges with four equivalent O(3)Li3NbV2 octahedra, and edges with four equivalent O(4)Li3NbV2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Li(4), one Nb(1), one V(2), and one V(3) atom to form OLi3NbV2 octahedra that share corners with six equivalent O(2)Li3NbV2 octahedra, edges with four equivalent O(3)Li3NbV2 octahedra, edges with four equivalent O(4)Li3NbV2 octahedra, and edges with four equivalent O(1)Li3V3 octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(4), one Nb(1), one V(1), and one V(3) atom to form OLi3NbV2 octahedra that share corners with six equivalent O(3)Li3NbV2 octahedra, edges with four equivalent O(2)Li3NbV2 octahedra, edges with four equivalent O(4)Li3NbV2 octahedra, and edges with four equivalent O(1)Li3V3 octahedra. The corner-sharing octahedra are not tilted. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Nb(1), one V(1), and one V(2) atom to form OLi3NbV2 octahedra that share corners with six equivalent O(4)Li3NbV2 octahedra, edges with four equivalent O(2)Li3NbV2 octahedra, edges with four equivalent O(3)Li3NbV2 octahedra, and edges with four equivalent O(1)Li3V3 octahedra. The corner-sharing octahedra are not tilted.
Li4NbV3O8 is alpha Po-derived structured and crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Nb(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. Both Li(1)-O(2) bond lengths are 2.19 Å. Both Li(1)-O(3) bond lengths are 2.18 Å. Both Li(1)-O(4) bond lengths are 2.16 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. Both Li(2)-O(1) bond lengths are 2.25 Å. Both Li(2)-O(3) bond lengths are 2.19 Å. Both Li(2)-O(4) bond lengths are 2.16 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. Both Li(3)-O(1) bond lengths are 2.24 Å. Both Li(3)-O(2) bond lengths are 2.19 Å. Both Li(3)-O(4) bond lengths are 2.17 Å. In the fourth Li site, Li(4) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. Both Li(4)-O(1) bond lengths are 2.15 Å. Both Li(4)-O(2) bond lengths are 2.13 Å. Both Li(4)-O(3) bond lengths are 2.14 Å. Nb(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form NbO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. Both Nb(1)-O(2) bond lengths are 2.10 Å. Both Nb(1)-O(3) bond lengths are 2.10 Å. Both Nb(1)-O(4) bond lengths are 2.11 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. Both V(1)-O(1) bond lengths are 2.04 Å. Both V(1)-O(3) bond lengths are 2.08 Å. Both V(1)-O(4) bond lengths are 2.11 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. Both V(2)-O(1) bond lengths are 2.04 Å. Both V(2)-O(2) bond lengths are 2.07 Å. Both V(2)-O(4) bond lengths are 2.12 Å. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. Both V(3)-O(1) bond lengths are 2.12 Å. Both V(3)-O(2) bond lengths are 2.15 Å. Both V(3)-O(3) bond lengths are 2.15 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Li(4), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with six equivalent O(1)Li3V3 octahedra, edges with four equivalent O(2)Li3NbV2 octahedra, edges with four equivalent O(3)Li3NbV2 octahedra, and edges with four equivalent O(4)Li3NbV2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Li(4), one Nb(1), one V(2), and one V(3) atom to form OLi3NbV2 octahedra that share corners with six equivalent O(2)Li3NbV2 octahedra, edges with four equivalent O(3)Li3NbV2 octahedra, edges with four equivalent O(4)Li3NbV2 octahedra, and edges with four equivalent O(1)Li3V3 octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(4), one Nb(1), one V(1), and one V(3) atom to form OLi3NbV2 octahedra that share corners with six equivalent O(3)Li3NbV2 octahedra, edges with four equivalent O(2)Li3NbV2 octahedra, edges with four equivalent O(4)Li3NbV2 octahedra, and edges with four equivalent O(1)Li3V3 octahedra. The corner-sharing octahedra are not tilted. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Nb(1), one V(1), and one V(2) atom to form OLi3NbV2 octahedra that share corners with six equivalent O(4)Li3NbV2 octahedra, edges with four equivalent O(2)Li3NbV2 octahedra, edges with four equivalent O(3)Li3NbV2 octahedra, and edges with four equivalent O(1)Li3V3 octahedra. The corner-sharing octahedra are not tilted.