Li2V3CuO8 is Hausmannite-derived structured and crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(6), and one O(7) atom to form LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(3)O6 octahedra, and corners with three equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-70°. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(1), one O(4), one O(5), and one O(8) atom. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form VO6 octahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Cu(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-60°. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form VO6 octahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Cu(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. In the third V site, V(3) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Cu(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. Cu(1) is bonded to one O(1), one O(2), one O(5), one O(6), one O(7), and one O(8) atom to form distorted CuO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-60°. There are eight inequivalent O sites. In the first O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), one V(2), and one Cu(1) atom. In the second O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), one V(3), and one Cu(1) atom. In the third O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(2), and one Cu(1) atom. In the fourth O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one V(3) atom. In the fifth O site, O(4) is bonded to one Li(2), one V(1), one V(2), and one V(3) atom to form distorted corner-sharing OLiV3 tetrahedra. In the sixth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), one V(3), and one Cu(1) atom. In the seventh O site, O(6) is bonded to one Li(1), one V(1), one V(3), and one Cu(1) atom to form corner-sharing OLiV2Cu tetrahedra. In the eighth O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(2), one V(3), and one Cu(1) atom.
Li2V3CuO8 is Hausmannite-derived structured and crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(6), and one O(7) atom to form LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(3)O6 octahedra, and corners with three equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-70°. The Li(1)-O(2) bond length is 1.97 Å. The Li(1)-O(3) bond length is 2.00 Å. The Li(1)-O(6) bond length is 2.01 Å. The Li(1)-O(7) bond length is 1.98 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(1), one O(4), one O(5), and one O(8) atom. The Li(2)-O(1) bond length is 1.94 Å. The Li(2)-O(4) bond length is 1.81 Å. The Li(2)-O(5) bond length is 1.98 Å. The Li(2)-O(8) bond length is 1.95 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form VO6 octahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Cu(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-60°. The V(1)-O(1) bond length is 1.95 Å. The V(1)-O(2) bond length is 1.80 Å. The V(1)-O(3) bond length is 2.02 Å. The V(1)-O(4) bond length is 1.98 Å. The V(1)-O(6) bond length is 2.13 Å. The V(1)-O(8) bond length is 2.00 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form VO6 octahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Cu(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. The V(2)-O(2) bond length is 2.08 Å. The V(2)-O(3) bond length is 2.00 Å. The V(2)-O(4) bond length is 1.98 Å. The V(2)-O(5) bond length is 2.07 Å. The V(2)-O(7) bond length is 1.79 Å. The V(2)-O(8) bond length is 1.94 Å. In the third V site, V(3) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share corners with two equivalent Cu(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Cu(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. The V(3)-O(1) bond length is 1.97 Å. The V(3)-O(3) bond length is 2.00 Å. The V(3)-O(4) bond length is 1.99 Å. The V(3)-O(5) bond length is 1.93 Å. The V(3)-O(6) bond length is 1.86 Å. The V(3)-O(7) bond length is 2.11 Å. Cu(1) is bonded to one O(1), one O(2), one O(5), one O(6), one O(7), and one O(8) atom to form distorted CuO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-60°. The Cu(1)-O(1) bond length is 2.13 Å. The Cu(1)-O(2) bond length is 2.39 Å. The Cu(1)-O(5) bond length is 2.01 Å. The Cu(1)-O(6) bond length is 2.09 Å. The Cu(1)-O(7) bond length is 2.36 Å. The Cu(1)-O(8) bond length is 2.09 Å. There are eight inequivalent O sites. In the first O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), one V(2), and one Cu(1) atom. In the second O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), one V(3), and one Cu(1) atom. In the third O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(2), and one Cu(1) atom. In the fourth O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one V(3) atom. In the fifth O site, O(4) is bonded to one Li(2), one V(1), one V(2), and one V(3) atom to form distorted corner-sharing OLiV3 tetrahedra. In the sixth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), one V(3), and one Cu(1) atom. In the seventh O site, O(6) is bonded to one Li(1), one V(1), one V(3), and one Cu(1) atom to form corner-sharing OLiV2Cu tetrahedra. In the eighth O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(2), one V(3), and one Cu(1) atom.