Li4Nb3V3(NiO8)2 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, and corners with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-68°. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(5), one O(7), and two equivalent O(11) atoms. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(4), one O(8), and two equivalent O(1) atoms. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Nb(2)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra, and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-62°. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form NbO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. In the second Nb site, Nb(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form NbO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra, edges with two equivalent Nb(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form VO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. In the second V site, V(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form VO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra, and edges with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent Nb(2)O6 octahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. In the second Ni site, Ni(2) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form distorted NiO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent V(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Nb(2), one V(2), and one Ni(1) atom to form distorted OLiNbVNi trigonal pyramids that share  a cornercorner with one O(12)LiNb2Ni tetrahedra,  a cornercorner with one O(4)LiNbV2 tetrahedra,  a cornercorner with one O(2)LiV2Ni tetrahedra, corners with three equivalent O(9)LiNbVNi tetrahedra,  a cornercorner with one O(1)LiNbVNi trigonal pyramid,  an edgeedge with one O(5)LiNb2V tetrahedra, and  an edgeedge with one O(1)LiNbVNi trigonal pyramid. In the second O site, O(2) is bonded to one Li(4), two equivalent V(1), and one Ni(1) atom to form distorted OLiV2Ni tetrahedra that share corners with two equivalent O(4)LiNbV2 tetrahedra, corners with two equivalent O(1)LiNbVNi trigonal pyramids, and corners with two equivalent O(7)LiV2Ni trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Nb(1), and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one Nb(1), and two equivalent V(1) atoms to form distorted OLiNbV2 tetrahedra that share corners with two equivalent O(2)LiV2Ni tetrahedra, corners with two equivalent O(1)LiNbVNi trigonal pyramids, and  an edgeedge with one O(7)LiV2Ni trigonal pyramid. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Nb(2), and one V(2) atom to form distorted OLiNb2V tetrahedra that share corners with two equivalent O(12)LiNb2Ni tetrahedra, corners with four equivalent O(9)LiNbVNi tetrahedra,  a cornercorner with one O(7)LiV2Ni trigonal pyramid, and edges with two equivalent O(1)LiNbVNi trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Nb(1), one V(1), and one Ni(1) atom. In the seventh O site, O(7) is bonded to one Li(2), two equivalent V(1), and one Ni(2) atom to form distorted OLiV2Ni trigonal pyramids that share  a cornercorner with one O(12)LiNb2Ni tetrahedra,  a cornercorner with one O(5)LiNb2V tetrahedra, corners with two equivalent O(9)LiNbVNi tetrahedra, corners with two equivalent O(2)LiV2Ni tetrahedra, and  an edgeedge with one O(4)LiNbV2 tetrahedra. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), two equivalent Nb(2), and one Ni(1) atom. In the ninth O site, O(9) is bonded to one Li(1), one Nb(2), one V(2), and one Ni(2) atom to form distorted OLiNbVNi tetrahedra that share  a cornercorner with one O(12)LiNb2Ni tetrahedra,  a cornercorner with one O(9)LiNbVNi tetrahedra, corners with two equivalent O(5)LiNb2V tetrahedra,  a cornercorner with one O(7)LiV2Ni trigonal pyramid, corners with three equivalent O(1)LiNbVNi trigonal pyramids,  an edgeedge with one O(12)LiNb2Ni tetrahedra, and  an edgeedge with one O(9)LiNbVNi tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent Nb(2), and one V(2) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one Nb(1), one V(1), and one Ni(2) atom. In the twelfth O site, O(12) is bonded to one Li(1), two equivalent Nb(2), and one Ni(2) atom to form distorted OLiNb2Ni tetrahedra that share corners with two equivalent O(5)LiNb2V tetrahedra, corners with two equivalent O(9)LiNbVNi tetrahedra,  a cornercorner with one O(7)LiV2Ni trigonal pyramid, corners with two equivalent O(1)LiNbVNi trigonal pyramids, and edges with two equivalent O(9)LiNbVNi tetrahedra.
Li4Nb3V3(NiO8)2 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one Nb(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, and corners with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-68°. The Li(1)-O(12) bond length is 2.04 Å. The Li(1)-O(3) bond length is 1.96 Å. Both Li(1)-O(9) bond lengths are 2.05 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(5), one O(7), and two equivalent O(11) atoms. The Li(2)-O(5) bond length is 1.84 Å. The Li(2)-O(7) bond length is 1.92 Å. Both Li(2)-O(11) bond lengths are 1.99 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(4), one O(8), and two equivalent O(1) atoms. The Li(3)-O(4) bond length is 1.77 Å. The Li(3)-O(8) bond length is 2.09 Å. Both Li(3)-O(1) bond lengths are 1.97 Å. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Nb(2)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra, and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-62°. The Li(4)-O(10) bond length is 2.13 Å. The Li(4)-O(2) bond length is 2.01 Å. Both Li(4)-O(6) bond lengths are 1.99 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form NbO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. The Nb(1)-O(3) bond length is 2.03 Å. The Nb(1)-O(4) bond length is 2.01 Å. Both Nb(1)-O(11) bond lengths are 2.08 Å. Both Nb(1)-O(6) bond lengths are 2.01 Å. In the second Nb site, Nb(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form NbO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra, edges with two equivalent Nb(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. The Nb(2)-O(1) bond length is 2.04 Å. The Nb(2)-O(10) bond length is 2.06 Å. The Nb(2)-O(12) bond length is 2.04 Å. The Nb(2)-O(5) bond length is 2.05 Å. The Nb(2)-O(8) bond length is 2.05 Å. The Nb(2)-O(9) bond length is 1.97 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form VO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. The V(1)-O(11) bond length is 2.05 Å. The V(1)-O(2) bond length is 2.01 Å. The V(1)-O(3) bond length is 2.09 Å. The V(1)-O(4) bond length is 2.06 Å. The V(1)-O(6) bond length is 2.08 Å. The V(1)-O(7) bond length is 2.02 Å. In the second V site, V(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form VO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra, and edges with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. The V(2)-O(10) bond length is 2.12 Å. The V(2)-O(5) bond length is 2.07 Å. Both V(2)-O(1) bond lengths are 2.02 Å. Both V(2)-O(9) bond lengths are 2.06 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent Nb(2)O6 octahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. The Ni(1)-O(2) bond length is 2.11 Å. The Ni(1)-O(8) bond length is 2.25 Å. Both Ni(1)-O(1) bond lengths are 2.19 Å. Both Ni(1)-O(6) bond lengths are 2.14 Å. In the second Ni site, Ni(2) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form distorted NiO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent V(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. The Ni(2)-O(12) bond length is 2.40 Å. The Ni(2)-O(7) bond length is 2.03 Å. Both Ni(2)-O(11) bond lengths are 2.07 Å. Both Ni(2)-O(9) bond lengths are 2.34 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Nb(2), one V(2), and one Ni(1) atom to form distorted OLiNbVNi trigonal pyramids that share  a cornercorner with one O(12)LiNb2Ni tetrahedra,  a cornercorner with one O(4)LiNbV2 tetrahedra,  a cornercorner with one O(2)LiV2Ni tetrahedra, corners with three equivalent O(9)LiNbVNi tetrahedra,  a cornercorner with one O(1)LiNbVNi trigonal pyramid,  an edgeedge with one O(5)LiNb2V tetrahedra, and  an edgeedge with one O(1)LiNbVNi trigonal pyramid. In the second O site, O(2) is bonded to one Li(4), two equivalent V(1), and one Ni(1) atom to form distorted OLiV2Ni tetrahedra that share corners with two equivalent O(4)LiNbV2 tetrahedra, corners with two equivalent O(1)LiNbVNi trigonal pyramids, and corners with two equivalent O(7)LiV2Ni trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Nb(1), and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one Nb(1), and two equivalent V(1) atoms to form distorted OLiNbV2 tetrahedra that share corners with two equivalent O(2)LiV2Ni tetrahedra, corners with two equivalent O(1)LiNbVNi trigonal pyramids, and  an edgeedge with one O(7)LiV2Ni trigonal pyramid. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Nb(2), and one V(2) atom to form distorted OLiNb2V tetrahedra that share corners with two equivalent O(12)LiNb2Ni tetrahedra, corners with four equivalent O(9)LiNbVNi tetrahedra,  a cornercorner with one O(7)LiV2Ni trigonal pyramid, and edges with two equivalent O(1)LiNbVNi trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Nb(1), one V(1), and one Ni(1) atom. In the seventh O site, O(7) is bonded to one Li(2), two equivalent V(1), and one Ni(2) atom to form distorted OLiV2Ni trigonal pyramids that share  a cornercorner with one O(12)LiNb2Ni tetrahedra,  a cornercorner with one O(5)LiNb2V tetrahedra, corners with two equivalent O(9)LiNbVNi tetrahedra, corners with two equivalent O(2)LiV2Ni tetrahedra, and  an edgeedge with one O(4)LiNbV2 tetrahedra. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), two equivalent Nb(2), and one Ni(1) atom. In the ninth O site, O(9) is bonded to one Li(1), one Nb(2), one V(2), and one Ni(2) atom to form distorted OLiNbVNi tetrahedra that share  a cornercorner with one O(12)LiNb2Ni tetrahedra,  a cornercorner with one O(9)LiNbVNi tetrahedra, corners with two equivalent O(5)LiNb2V tetrahedra,  a cornercorner with one O(7)LiV2Ni trigonal pyramid, corners with three equivalent O(1)LiNbVNi trigonal pyramids,  an edgeedge with one O(12)LiNb2Ni tetrahedra, and  an edgeedge with one O(9)LiNbVNi tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent Nb(2), and one V(2) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one Nb(1), one V(1), and one Ni(2) atom. In the twelfth O site, O(12) is bonded to one Li(1), two equivalent Nb(2), and one Ni(2) atom to form distorted OLiNb2Ni tetrahedra that share corners with two equivalent O(5)LiNb2V tetrahedra, corners with two equivalent O(9)LiNbVNi tetrahedra,  a cornercorner with one O(7)LiV2Ni trigonal pyramid, corners with two equivalent O(1)LiNbVNi trigonal pyramids, and edges with two equivalent O(9)LiNbVNi tetrahedra.