Li3V2(NiO4)2 crystallizes in the monoclinic C2/m space group. There are two 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(3) atoms to form LiO6 octahedra that share corners with six equivalent Ni(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)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 10-11°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the second V site, V(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form VO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)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 10-11°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one V(1), and two equivalent Ni(1) atoms to form OLi3VNi2 octahedra that share corners with six equivalent O(1)Li3VNi2 octahedra, edges with four equivalent O(2)Li2VNi2 square pyramids, and edges with eight equivalent O(3)Li2V2Ni square pyramids. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to two equivalent Li(1), one V(2), and two equivalent Ni(1) atoms to form OLi2VNi2 square pyramids that share corners with four equivalent O(3)Li2V2Ni square pyramids, corners with five equivalent O(2)Li2VNi2 square pyramids, edges with four equivalent O(1)Li3VNi2 octahedra, and edges with four equivalent O(3)Li2V2Ni square pyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one Ni(1) atom to form OLi2V2Ni square pyramids that share corners with two equivalent O(2)Li2VNi2 square pyramids, corners with seven equivalent O(3)Li2V2Ni square pyramids, edges with four equivalent O(1)Li3VNi2 octahedra, edges with two equivalent O(3)Li2V2Ni square pyramids, and edges with two equivalent O(2)Li2VNi2 square pyramids.
Li3V2(NiO4)2 crystallizes in the monoclinic C2/m space group. There are two 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(3) atoms to form LiO6 octahedra that share corners with six equivalent Ni(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)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 10-11°. Both Li(1)-O(1) bond lengths are 2.13 Å. Both Li(1)-O(2) bond lengths are 2.13 Å. Both Li(1)-O(3) bond lengths are 2.08 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. Both Li(2)-O(1) bond lengths are 2.26 Å. All Li(2)-O(3) bond lengths are 2.17 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. Both V(1)-O(1) bond lengths are 1.90 Å. All V(1)-O(3) bond lengths are 2.04 Å. In the second V site, V(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form VO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. Both V(2)-O(2) bond lengths are 1.87 Å. All V(2)-O(3) bond lengths are 1.92 Å. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)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 10-11°. Both Ni(1)-O(1) bond lengths are 2.08 Å. Both Ni(1)-O(2) bond lengths are 2.08 Å. Both Ni(1)-O(3) bond lengths are 2.10 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one V(1), and two equivalent Ni(1) atoms to form OLi3VNi2 octahedra that share corners with six equivalent O(1)Li3VNi2 octahedra, edges with four equivalent O(2)Li2VNi2 square pyramids, and edges with eight equivalent O(3)Li2V2Ni square pyramids. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to two equivalent Li(1), one V(2), and two equivalent Ni(1) atoms to form OLi2VNi2 square pyramids that share corners with four equivalent O(3)Li2V2Ni square pyramids, corners with five equivalent O(2)Li2VNi2 square pyramids, edges with four equivalent O(1)Li3VNi2 octahedra, and edges with four equivalent O(3)Li2V2Ni square pyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one V(1), one V(2), and one Ni(1) atom to form OLi2V2Ni square pyramids that share corners with two equivalent O(2)Li2VNi2 square pyramids, corners with seven equivalent O(3)Li2V2Ni square pyramids, edges with four equivalent O(1)Li3VNi2 octahedra, edges with two equivalent O(3)Li2V2Ni square pyramids, and edges with two equivalent O(2)Li2VNi2 square pyramids.