Li4V3NiO8 is beta Sn-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(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Ni(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 are 13°. In the second Li site, Li(2) 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(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 V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-16°. In the third Li site, Li(3) 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 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 V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-15°. In the fourth Li site, Li(4) 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(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 V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. There are three inequivalent V sites. In the first V site, V(1) 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(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 V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-16°. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(3), 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 V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-15°. In the third V site, V(3) 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(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 V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form NiO6 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 are 13°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(4), one V(1), one V(3), and one Ni(1) atom to form OLi3V2Ni octahedra that share corners with six equivalent O(1)Li3V2Ni octahedra, edges with four equivalent O(2)Li3V2Ni octahedra, edges with four equivalent O(4)Li3V2Ni octahedra, and edges with four equivalent O(3)Li3V3 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one Ni(1) atom to form distorted OLi3V2Ni octahedra that share corners with six equivalent O(2)Li3V2Ni octahedra, edges with four equivalent O(1)Li3V2Ni octahedra, edges with four equivalent O(4)Li3V2Ni octahedra, and edges with four equivalent O(3)Li3V3 octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) 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 distorted OLi3V3 octahedra that share corners with six equivalent O(3)Li3V3 octahedra, edges with four equivalent O(1)Li3V2Ni octahedra, edges with four equivalent O(2)Li3V2Ni octahedra, and edges with four equivalent O(4)Li3V2Ni octahedra. The corner-sharing octahedra are not tilted. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Li(4), one V(2), one V(3), and one Ni(1) atom to form distorted OLi3V2Ni octahedra that share corners with six equivalent O(4)Li3V2Ni octahedra, edges with four equivalent O(1)Li3V2Ni octahedra, edges with four equivalent O(2)Li3V2Ni octahedra, and edges with four equivalent O(3)Li3V3 octahedra. The corner-sharing octahedra are not tilted.
Li4V3NiO8 is beta Sn-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(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Ni(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 are 13°. Both Li(1)-O(1) bond lengths are 2.13 Å. Both Li(1)-O(2) bond lengths are 2.35 Å. Both Li(1)-O(4) bond lengths are 2.02 Å. In the second Li site, Li(2) 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(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 V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-16°. Both Li(2)-O(1) bond lengths are 2.33 Å. Both Li(2)-O(2) bond lengths are 2.26 Å. Both Li(2)-O(3) bond lengths are 2.06 Å. In the third Li site, Li(3) 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 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 V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-15°. Both Li(3)-O(2) bond lengths are 1.95 Å. Both Li(3)-O(3) bond lengths are 2.11 Å. Both Li(3)-O(4) bond lengths are 2.35 Å. In the fourth Li site, Li(4) 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(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 V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. Both Li(4)-O(1) bond lengths are 2.02 Å. Both Li(4)-O(3) bond lengths are 2.38 Å. Both Li(4)-O(4) bond lengths are 2.18 Å. There are three inequivalent V sites. In the first V site, V(1) 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(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 V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-16°. Both V(1)-O(1) bond lengths are 1.91 Å. Both V(1)-O(2) bond lengths are 1.96 Å. Both V(1)-O(3) bond lengths are 2.21 Å. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(3), 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 V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-15°. Both V(2)-O(2) bond lengths are 2.32 Å. Both V(2)-O(3) bond lengths are 2.10 Å. Both V(2)-O(4) bond lengths are 1.88 Å. In the third V site, V(3) 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(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 V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. Both V(3)-O(1) bond lengths are 2.24 Å. Both V(3)-O(3) bond lengths are 1.85 Å. Both V(3)-O(4) bond lengths are 2.03 Å. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form NiO6 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 are 13°. Both Ni(1)-O(1) bond lengths are 2.07 Å. Both Ni(1)-O(2) bond lengths are 1.90 Å. Both Ni(1)-O(4) bond lengths are 2.24 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(4), one V(1), one V(3), and one Ni(1) atom to form OLi3V2Ni octahedra that share corners with six equivalent O(1)Li3V2Ni octahedra, edges with four equivalent O(2)Li3V2Ni octahedra, edges with four equivalent O(4)Li3V2Ni octahedra, and edges with four equivalent O(3)Li3V3 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one Ni(1) atom to form distorted OLi3V2Ni octahedra that share corners with six equivalent O(2)Li3V2Ni octahedra, edges with four equivalent O(1)Li3V2Ni octahedra, edges with four equivalent O(4)Li3V2Ni octahedra, and edges with four equivalent O(3)Li3V3 octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) 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 distorted OLi3V3 octahedra that share corners with six equivalent O(3)Li3V3 octahedra, edges with four equivalent O(1)Li3V2Ni octahedra, edges with four equivalent O(2)Li3V2Ni octahedra, and edges with four equivalent O(4)Li3V2Ni octahedra. The corner-sharing octahedra are not tilted. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Li(4), one V(2), one V(3), and one Ni(1) atom to form distorted OLi3V2Ni octahedra that share corners with six equivalent O(4)Li3V2Ni octahedra, edges with four equivalent O(1)Li3V2Ni octahedra, edges with four equivalent O(2)Li3V2Ni octahedra, and edges with four equivalent O(3)Li3V3 octahedra. The corner-sharing octahedra are not tilted.