Li2V3NiO8 crystallizes in the monoclinic Cm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(8), and two equivalent O(5) atoms to form LiO5 square pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and  an edgeedge with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 3-14°. In the second Li site, Li(2) is bonded to one O(1), one O(7), one O(8), and two equivalent O(4) atoms to form LiO5 square pyramids that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(2)O5 square pyramids,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles are 1°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(8) atoms to form VO6 octahedra that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, and edges with two equivalent Li(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 5-17°. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(4), one O(5), one O(6), one O(7), and two equivalent O(1) atoms. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(7) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra,  an edgeedge with one Li(1)O5 square pyramid, and edges with two equivalent Li(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 5-21°. Ni(1) is bonded to one O(5), one O(6), one O(7), one O(8), and two equivalent O(2) atoms to form NiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(2)O5 square pyramid, and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 17-22°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(3), and two equivalent V(2) atoms to form OLi2V3 trigonal bipyramids that share  a cornercorner with one O(4)Li2V3 trigonal bipyramid,  a cornercorner with one O(7)LiV3Ni trigonal bipyramid, corners with two equivalent O(1)Li2V3 trigonal bipyramids,  an edgeedge with one O(8)Li2V2Ni square pyramid,  an edgeedge with one O(2)LiV2Ni2 square pyramid, edges with two equivalent O(5)Li2V2Ni square pyramids, edges with two equivalent O(4)Li2V3 trigonal bipyramids, and edges with two equivalent O(7)LiV3Ni trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(3), and two equivalent Ni(1) atoms to form OLiV2Ni2 square pyramids that share  a cornercorner with one O(5)Li2V2Ni square pyramid,  a cornercorner with one O(8)Li2V2Ni square pyramid, corners with two equivalent O(2)LiV2Ni2 square pyramids, edges with two equivalent O(5)Li2V2Ni square pyramids, edges with two equivalent O(8)Li2V2Ni square pyramids,  an edgeedge with one O(1)Li2V3 trigonal bipyramid,  an edgeedge with one O(4)Li2V3 trigonal bipyramid, and edges with two equivalent O(7)LiV3Ni trigonal bipyramids. In the third O site, O(3) is bonded in a linear geometry to one V(1) and one V(3) atom. In the fourth O site, O(4) is bonded to two equivalent Li(2), one V(1), one V(2), and one V(3) atom to form OLi2V3 trigonal bipyramids that share  a cornercorner with one O(1)Li2V3 trigonal bipyramid,  a cornercorner with one O(7)LiV3Ni trigonal bipyramid, corners with two equivalent O(4)Li2V3 trigonal bipyramids,  an edgeedge with one O(5)Li2V2Ni square pyramid,  an edgeedge with one O(2)LiV2Ni2 square pyramid, edges with two equivalent O(8)Li2V2Ni square pyramids, edges with two equivalent O(1)Li2V3 trigonal bipyramids, and edges with two equivalent O(7)LiV3Ni trigonal bipyramids. In the fifth O site, O(5) is bonded to two equivalent Li(1), one V(1), one V(2), and one Ni(1) atom to form distorted OLi2V2Ni square pyramids that share  a cornercorner with one O(8)Li2V2Ni square pyramid,  a cornercorner with one O(2)LiV2Ni2 square pyramid, corners with two equivalent O(5)Li2V2Ni square pyramids, edges with two equivalent O(8)Li2V2Ni square pyramids, edges with two equivalent O(2)LiV2Ni2 square pyramids,  an edgeedge with one O(4)Li2V3 trigonal bipyramid,  an edgeedge with one O(7)LiV3Ni trigonal bipyramid, and edges with two equivalent O(1)Li2V3 trigonal bipyramids. In the sixth O site, O(6) is bonded in a linear geometry to one V(2) and one Ni(1) atom. In the seventh O site, O(7) is bonded to one Li(2), one V(2), two equivalent V(3), and one Ni(1) atom to form OLiV3Ni trigonal bipyramids that share  a cornercorner with one O(1)Li2V3 trigonal bipyramid,  a cornercorner with one O(4)Li2V3 trigonal bipyramid, corners with two equivalent O(7)LiV3Ni trigonal bipyramids,  an edgeedge with one O(5)Li2V2Ni square pyramid,  an edgeedge with one O(8)Li2V2Ni square pyramid, edges with two equivalent O(2)LiV2Ni2 square pyramids, edges with two equivalent O(1)Li2V3 trigonal bipyramids, and edges with two equivalent O(4)Li2V3 trigonal bipyramids. In the eighth O site, O(8) is bonded to one Li(1), one Li(2), two equivalent V(1), and one Ni(1) atom to form OLi2V2Ni square pyramids that share  a cornercorner with one O(5)Li2V2Ni square pyramid,  a cornercorner with one O(2)LiV2Ni2 square pyramid, corners with two equivalent O(8)Li2V2Ni square pyramids, edges with two equivalent O(5)Li2V2Ni square pyramids, edges with two equivalent O(2)LiV2Ni2 square pyramids,  an edgeedge with one O(1)Li2V3 trigonal bipyramid,  an edgeedge with one O(7)LiV3Ni trigonal bipyramid, and edges with two equivalent O(4)Li2V3 trigonal bipyramids.
Li2V3NiO8 crystallizes in the monoclinic Cm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(8), and two equivalent O(5) atoms to form LiO5 square pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and  an edgeedge with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 3-14°. The Li(1)-O(1) bond length is 2.04 Å. The Li(1)-O(2) bond length is 2.15 Å. The Li(1)-O(8) bond length is 2.08 Å. Both Li(1)-O(5) bond lengths are 2.02 Å. In the second Li site, Li(2) is bonded to one O(1), one O(7), one O(8), and two equivalent O(4) atoms to form LiO5 square pyramids that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(2)O5 square pyramids,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles are 1°. The Li(2)-O(1) bond length is 2.14 Å. The Li(2)-O(7) bond length is 2.17 Å. The Li(2)-O(8) bond length is 1.99 Å. Both Li(2)-O(4) bond lengths are 2.01 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(8) atoms to form VO6 octahedra that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, and edges with two equivalent Li(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 5-17°. The V(1)-O(2) bond length is 1.99 Å. The V(1)-O(3) bond length is 1.94 Å. The V(1)-O(4) bond length is 2.12 Å. The V(1)-O(5) bond length is 1.81 Å. Both V(1)-O(8) bond lengths are 2.02 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(4), one O(5), one O(6), one O(7), and two equivalent O(1) atoms. The V(2)-O(4) bond length is 1.99 Å. The V(2)-O(5) bond length is 2.32 Å. The V(2)-O(6) bond length is 1.67 Å. The V(2)-O(7) bond length is 2.03 Å. Both V(2)-O(1) bond lengths are 2.05 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(7) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra,  an edgeedge with one Li(1)O5 square pyramid, and edges with two equivalent Li(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 5-21°. The V(3)-O(1) bond length is 1.99 Å. The V(3)-O(2) bond length is 2.16 Å. The V(3)-O(3) bond length is 1.73 Å. The V(3)-O(4) bond length is 2.00 Å. Both V(3)-O(7) bond lengths are 2.04 Å. Ni(1) is bonded to one O(5), one O(6), one O(7), one O(8), and two equivalent O(2) atoms to form NiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(2)O5 square pyramid, and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 17-22°. The Ni(1)-O(5) bond length is 2.10 Å. The Ni(1)-O(6) bond length is 1.97 Å. The Ni(1)-O(7) bond length is 2.16 Å. The Ni(1)-O(8) bond length is 2.09 Å. Both Ni(1)-O(2) bond lengths are 2.05 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(3), and two equivalent V(2) atoms to form OLi2V3 trigonal bipyramids that share  a cornercorner with one O(4)Li2V3 trigonal bipyramid,  a cornercorner with one O(7)LiV3Ni trigonal bipyramid, corners with two equivalent O(1)Li2V3 trigonal bipyramids,  an edgeedge with one O(8)Li2V2Ni square pyramid,  an edgeedge with one O(2)LiV2Ni2 square pyramid, edges with two equivalent O(5)Li2V2Ni square pyramids, edges with two equivalent O(4)Li2V3 trigonal bipyramids, and edges with two equivalent O(7)LiV3Ni trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(3), and two equivalent Ni(1) atoms to form OLiV2Ni2 square pyramids that share  a cornercorner with one O(5)Li2V2Ni square pyramid,  a cornercorner with one O(8)Li2V2Ni square pyramid, corners with two equivalent O(2)LiV2Ni2 square pyramids, edges with two equivalent O(5)Li2V2Ni square pyramids, edges with two equivalent O(8)Li2V2Ni square pyramids,  an edgeedge with one O(1)Li2V3 trigonal bipyramid,  an edgeedge with one O(4)Li2V3 trigonal bipyramid, and edges with two equivalent O(7)LiV3Ni trigonal bipyramids. In the third O site, O(3) is bonded in a linear geometry to one V(1) and one V(3) atom. In the fourth O site, O(4) is bonded to two equivalent Li(2), one V(1), one V(2), and one V(3) atom to form OLi2V3 trigonal bipyramids that share  a cornercorner with one O(1)Li2V3 trigonal bipyramid,  a cornercorner with one O(7)LiV3Ni trigonal bipyramid, corners with two equivalent O(4)Li2V3 trigonal bipyramids,  an edgeedge with one O(5)Li2V2Ni square pyramid,  an edgeedge with one O(2)LiV2Ni2 square pyramid, edges with two equivalent O(8)Li2V2Ni square pyramids, edges with two equivalent O(1)Li2V3 trigonal bipyramids, and edges with two equivalent O(7)LiV3Ni trigonal bipyramids. In the fifth O site, O(5) is bonded to two equivalent Li(1), one V(1), one V(2), and one Ni(1) atom to form distorted OLi2V2Ni square pyramids that share  a cornercorner with one O(8)Li2V2Ni square pyramid,  a cornercorner with one O(2)LiV2Ni2 square pyramid, corners with two equivalent O(5)Li2V2Ni square pyramids, edges with two equivalent O(8)Li2V2Ni square pyramids, edges with two equivalent O(2)LiV2Ni2 square pyramids,  an edgeedge with one O(4)Li2V3 trigonal bipyramid,  an edgeedge with one O(7)LiV3Ni trigonal bipyramid, and edges with two equivalent O(1)Li2V3 trigonal bipyramids. In the sixth O site, O(6) is bonded in a linear geometry to one V(2) and one Ni(1) atom. In the seventh O site, O(7) is bonded to one Li(2), one V(2), two equivalent V(3), and one Ni(1) atom to form OLiV3Ni trigonal bipyramids that share  a cornercorner with one O(1)Li2V3 trigonal bipyramid,  a cornercorner with one O(4)Li2V3 trigonal bipyramid, corners with two equivalent O(7)LiV3Ni trigonal bipyramids,  an edgeedge with one O(5)Li2V2Ni square pyramid,  an edgeedge with one O(8)Li2V2Ni square pyramid, edges with two equivalent O(2)LiV2Ni2 square pyramids, edges with two equivalent O(1)Li2V3 trigonal bipyramids, and edges with two equivalent O(4)Li2V3 trigonal bipyramids. In the eighth O site, O(8) is bonded to one Li(1), one Li(2), two equivalent V(1), and one Ni(1) atom to form OLi2V2Ni square pyramids that share  a cornercorner with one O(5)Li2V2Ni square pyramid,  a cornercorner with one O(2)LiV2Ni2 square pyramid, corners with two equivalent O(8)Li2V2Ni square pyramids, edges with two equivalent O(5)Li2V2Ni square pyramids, edges with two equivalent O(2)LiV2Ni2 square pyramids,  an edgeedge with one O(1)Li2V3 trigonal bipyramid,  an edgeedge with one O(7)LiV3Ni trigonal bipyramid, and edges with two equivalent O(4)Li2V3 trigonal bipyramids.