Li3V4CuO12 crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and edges with two equivalent Cu(1)O6 octahedra. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to two equivalent O(2) and two equivalent O(3) atoms. In the third Li site, Li(3) is bonded in a distorted see-saw-like geometry to two equivalent O(1) and two equivalent O(6) atoms. There are two inequivalent V sites. In the first V site, V(1) 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 Cu(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-64°. In the second V site, V(2) 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 Li(1)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra, and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-62°. Cu(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form CuO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. 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 Li(3), one V(1), and one Cu(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(2), and one Cu(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(3), one V(2), and one Cu(1) atom.
Li3V4CuO12 crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and edges with two equivalent Cu(1)O6 octahedra. Both Li(1)-O(1) bond lengths are 2.33 Å. Both Li(1)-O(2) bond lengths are 2.08 Å. Both Li(1)-O(3) bond lengths are 2.25 Å. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to two equivalent O(2) and two equivalent O(3) atoms. Both Li(2)-O(2) bond lengths are 2.37 Å. Both Li(2)-O(3) bond lengths are 1.98 Å. In the third Li site, Li(3) is bonded in a distorted see-saw-like geometry to two equivalent O(1) and two equivalent O(6) atoms. Both Li(3)-O(1) bond lengths are 1.99 Å. Both Li(3)-O(6) bond lengths are 2.36 Å. There are two inequivalent V sites. In the first V site, V(1) 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 Cu(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-64°. The V(1)-O(1) bond length is 1.71 Å. The V(1)-O(2) bond length is 1.68 Å. The V(1)-O(4) bond length is 1.81 Å. The V(1)-O(5) bond length is 1.81 Å. In the second V site, V(2) 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 Li(1)O6 octahedra, corners with two equivalent Cu(1)O6 octahedra, and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-62°. The V(2)-O(3) bond length is 1.71 Å. The V(2)-O(4) bond length is 1.80 Å. The V(2)-O(5) bond length is 1.81 Å. The V(2)-O(6) bond length is 1.69 Å. Cu(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form CuO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. Both Cu(1)-O(1) bond lengths are 2.21 Å. Both Cu(1)-O(3) bond lengths are 2.27 Å. Both Cu(1)-O(6) bond lengths are 2.08 Å. 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 Li(3), one V(1), and one Cu(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(2), and one Cu(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(3), one V(2), and one Cu(1) atom.