Li2V5NiO12 is Esseneite-like structured and crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(6) 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)O4 tetrahedra, and edges with two equivalent Ni(1)O6 octahedra. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-63°. 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, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-62°. Ni(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(3)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(2), one V(1), one V(2), and one Ni(1) atom. 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 3-coordinate geometry to one Li(2), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one Li(1), one V(2), and one V(3) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one V(3), and one Ni(1) atom.
Li2V5NiO12 is Esseneite-like structured and crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. Both Li(1)-O(2) bond lengths are 2.42 Å. Both Li(1)-O(3) bond lengths are 2.02 Å. Both Li(1)-O(5) bond lengths are 2.61 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms. Both Li(2)-O(1) bond lengths are 2.04 Å. Both Li(2)-O(4) bond lengths are 2.50 Å. Both Li(2)-O(6) bond lengths are 2.45 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)O4 tetrahedra, and edges with two equivalent Ni(1)O6 octahedra. Both V(1)-O(1) bond lengths are 2.10 Å. Both V(1)-O(2) bond lengths are 1.96 Å. Both V(1)-O(3) bond lengths are 2.11 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-63°. The V(2)-O(1) bond length is 1.77 Å. The V(2)-O(2) bond length is 1.74 Å. The V(2)-O(4) bond length is 1.80 Å. The V(2)-O(5) bond length is 1.79 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, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-62°. The V(3)-O(3) bond length is 1.77 Å. The V(3)-O(4) bond length is 1.80 Å. The V(3)-O(5) bond length is 1.81 Å. The V(3)-O(6) bond length is 1.70 Å. Ni(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(3)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. Both Ni(1)-O(1) bond lengths are 2.24 Å. Both Ni(1)-O(3) bond lengths are 2.21 Å. Both Ni(1)-O(6) bond lengths are 1.96 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(2), one V(1), one V(2), and one Ni(1) atom. 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 3-coordinate geometry to one Li(2), one V(2), and one V(3) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one Li(1), one V(2), and one V(3) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one V(3), and one Ni(1) atom.