LiV2NiO6 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and one O(6) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(5), one O(6), and two equivalent O(4) atoms to form VO5 trigonal bipyramids that share corners with two equivalent Ni(1)O6 octahedra, corners with two equivalent V(2)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra, and  an edgeedge with one V(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 34-47°. In the second V site, V(2) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form distorted VO4 tetrahedra that share corners with three equivalent Ni(1)O6 octahedra and corners with two equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 16-66°. Ni(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form NiO6 octahedra that share corners with three equivalent V(2)O4 tetrahedra, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Ni(1)O6 octahedra, and  an edgeedge with one V(1)O5 trigonal bipyramid. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(2), and two equivalent Ni(1) atoms. In the second O site, O(2) is bonded to one Li(1), one V(1), and two equivalent Ni(1) atoms to form distorted edge-sharing OLiVNi2 tetrahedra. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one Ni(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent V(1) and one Ni(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom.
LiV2NiO6 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), one O(5), and one O(6) atom. The Li(1)-O(1) bond length is 2.10 Å. The Li(1)-O(2) bond length is 2.08 Å. The Li(1)-O(3) bond length is 2.49 Å. The Li(1)-O(5) bond length is 2.33 Å. The Li(1)-O(6) bond length is 2.03 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(5), one O(6), and two equivalent O(4) atoms to form VO5 trigonal bipyramids that share corners with two equivalent Ni(1)O6 octahedra, corners with two equivalent V(2)O4 tetrahedra,  an edgeedge with one Ni(1)O6 octahedra, and  an edgeedge with one V(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 34-47°. The V(1)-O(2) bond length is 1.77 Å. The V(1)-O(5) bond length is 1.96 Å. The V(1)-O(6) bond length is 1.91 Å. There is one shorter (1.79 Å) and one longer (2.16 Å) V(1)-O(4) bond length. In the second V site, V(2) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form distorted VO4 tetrahedra that share corners with three equivalent Ni(1)O6 octahedra and corners with two equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 16-66°. The V(2)-O(1) bond length is 1.78 Å. The V(2)-O(3) bond length is 1.68 Å. The V(2)-O(5) bond length is 1.78 Å. The V(2)-O(6) bond length is 1.80 Å. Ni(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form NiO6 octahedra that share corners with three equivalent V(2)O4 tetrahedra, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Ni(1)O6 octahedra, and  an edgeedge with one V(1)O5 trigonal bipyramid. The Ni(1)-O(3) bond length is 2.03 Å. The Ni(1)-O(4) bond length is 2.03 Å. There is one shorter (2.07 Å) and one longer (2.20 Å) Ni(1)-O(1) bond length. There is one shorter (2.01 Å) and one longer (2.17 Å) Ni(1)-O(2) bond length. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(2), and two equivalent Ni(1) atoms. In the second O site, O(2) is bonded to one Li(1), one V(1), and two equivalent Ni(1) atoms to form distorted edge-sharing OLiVNi2 tetrahedra. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one Ni(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent V(1) and one Ni(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom.