Li2V5NiO12 crystallizes in the monoclinic C2 space group. There are two 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(5) atoms to form distorted LiO6 pentagonal pyramids that share corners with four equivalent V(3)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O5 trigonal bipyramids. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(4) atoms. 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 two equivalent V(3)O4 tetrahedra, corners with four equivalent V(2)O5 trigonal bipyramids, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Li(1)O6 pentagonal pyramids. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), one O(5), and one O(6) atom to form VO5 trigonal bipyramids that share corners with two equivalent V(1)O6 octahedra, corners with three equivalent V(3)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra, and  an edgeedge with one Li(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 34-54°. In the third V site, V(3) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra, corners with two equivalent Li(1)O6 pentagonal pyramids, and corners with three equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 42-64°. Ni(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form distorted NiO6 octahedra that share corners with four equivalent V(3)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra,  an edgeedge with one Li(1)O6 pentagonal pyramid, and edges with two equivalent V(2)O5 trigonal bipyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one V(1), one V(2), and one Ni(1) atom to form a mixture of corner and edge-sharing OLiV2Ni tetrahedra. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the third O site, O(3) is bonded to one Li(1), one V(1), one V(3), and one Ni(1) atom to form a mixture of distorted corner and edge-sharing OLiV2Ni trigonal pyramids. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(2), one V(3), and one Ni(1) atom.
Li2V5NiO12 crystallizes in the monoclinic C2 space group. There are two 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(5) atoms to form distorted LiO6 pentagonal pyramids that share corners with four equivalent V(3)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O5 trigonal bipyramids. Both Li(1)-O(2) bond lengths are 2.34 Å. Both Li(1)-O(3) bond lengths are 2.17 Å. Both Li(1)-O(5) bond lengths are 2.30 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(4) atoms. Both Li(2)-O(1) bond lengths are 2.01 Å. Both Li(2)-O(4) bond lengths are 2.08 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 two equivalent V(3)O4 tetrahedra, corners with four equivalent V(2)O5 trigonal bipyramids, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Li(1)O6 pentagonal pyramids. Both V(1)-O(1) bond lengths are 2.03 Å. Both V(1)-O(2) bond lengths are 1.84 Å. Both V(1)-O(3) bond lengths are 2.08 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), one O(5), and one O(6) atom to form VO5 trigonal bipyramids that share corners with two equivalent V(1)O6 octahedra, corners with three equivalent V(3)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra, and  an edgeedge with one Li(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 34-54°. The V(2)-O(1) bond length is 1.90 Å. The V(2)-O(2) bond length is 1.88 Å. The V(2)-O(4) bond length is 1.98 Å. The V(2)-O(5) bond length is 2.04 Å. The V(2)-O(6) bond length is 2.24 Å. In the third V site, V(3) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Ni(1)O6 octahedra, corners with two equivalent Li(1)O6 pentagonal pyramids, and corners with three equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 42-64°. The V(3)-O(3) bond length is 1.78 Å. The V(3)-O(4) bond length is 1.76 Å. The V(3)-O(5) bond length is 1.73 Å. The V(3)-O(6) bond length is 1.74 Å. Ni(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form distorted NiO6 octahedra that share corners with four equivalent V(3)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra,  an edgeedge with one Li(1)O6 pentagonal pyramid, and edges with two equivalent V(2)O5 trigonal bipyramids. Both Ni(1)-O(1) bond lengths are 2.06 Å. Both Ni(1)-O(3) bond lengths are 2.16 Å. Both Ni(1)-O(6) bond lengths are 2.08 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one V(1), one V(2), and one Ni(1) atom to form a mixture of corner and edge-sharing OLiV2Ni tetrahedra. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the third O site, O(3) is bonded to one Li(1), one V(1), one V(3), and one Ni(1) atom to form a mixture of distorted corner and edge-sharing OLiV2Ni trigonal pyramids. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(2), one V(3), and one Ni(1) atom.