Li2V5CuO12 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(3) and two equivalent O(5) atoms. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form distorted LiO6 pentagonal pyramids that share corners with four equivalent V(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra,  an edgeedge with one Cu(1)O6 pentagonal pyramid, and edges with two equivalent V(3)O5 trigonal bipyramids. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(3)O5 trigonal bipyramids, edges with two equivalent Li(2)O6 pentagonal pyramids, and edges with two equivalent Cu(1)O6 pentagonal pyramids. 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 V(1)O6 octahedra, corners with two equivalent Li(2)O6 pentagonal pyramids, corners with two equivalent Cu(1)O6 pentagonal pyramids, and corners with three equivalent V(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 64°. In the third V site, V(3) is bonded to one O(2), one O(3), 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(2)O4 tetrahedra,  an edgeedge with one Li(2)O6 pentagonal pyramid, and  an edgeedge with one Cu(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 29-51°. Cu(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted CuO6 pentagonal pyramids that share corners with four equivalent V(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra,  an edgeedge with one Li(2)O6 pentagonal pyramid, and edges with two equivalent V(3)O5 trigonal bipyramids. 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 Cu(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Cu(1) atom. In the third O site, O(3) is bonded to one Li(1), one V(1), one V(3), and one Cu(1) atom to form a mixture of distorted edge and corner-sharing OLiV2Cu trigonal pyramids. In the fourth O site, O(4) is bonded in a distorted 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 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 Li(2), one V(1), and one V(3) atom.
Li2V5CuO12 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(3) and two equivalent O(5) atoms. Both Li(1)-O(3) bond lengths are 2.07 Å. Both Li(1)-O(5) bond lengths are 2.06 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form distorted LiO6 pentagonal pyramids that share corners with four equivalent V(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra,  an edgeedge with one Cu(1)O6 pentagonal pyramid, and edges with two equivalent V(3)O5 trigonal bipyramids. Both Li(2)-O(1) bond lengths are 2.18 Å. Both Li(2)-O(4) bond lengths are 2.35 Å. Both Li(2)-O(6) bond lengths are 2.35 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(3)O5 trigonal bipyramids, edges with two equivalent Li(2)O6 pentagonal pyramids, and edges with two equivalent Cu(1)O6 pentagonal pyramids. Both V(1)-O(1) bond lengths are 2.08 Å. Both V(1)-O(3) bond lengths are 2.02 Å. Both V(1)-O(6) bond lengths are 1.96 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 V(1)O6 octahedra, corners with two equivalent Li(2)O6 pentagonal pyramids, corners with two equivalent Cu(1)O6 pentagonal pyramids, and corners with three equivalent V(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 64°. The V(2)-O(1) bond length is 1.74 Å. The V(2)-O(2) bond length is 1.75 Å. The V(2)-O(4) bond length is 1.75 Å. The V(2)-O(5) bond length is 1.79 Å. In the third V site, V(3) is bonded to one O(2), one O(3), 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(2)O4 tetrahedra,  an edgeedge with one Li(2)O6 pentagonal pyramid, and  an edgeedge with one Cu(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 29-51°. The V(3)-O(2) bond length is 2.18 Å. The V(3)-O(3) bond length is 1.83 Å. The V(3)-O(4) bond length is 1.99 Å. The V(3)-O(5) bond length is 1.96 Å. The V(3)-O(6) bond length is 1.75 Å. Cu(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted CuO6 pentagonal pyramids that share corners with four equivalent V(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra,  an edgeedge with one Li(2)O6 pentagonal pyramid, and edges with two equivalent V(3)O5 trigonal bipyramids. Both Cu(1)-O(1) bond lengths are 2.28 Å. Both Cu(1)-O(2) bond lengths are 2.08 Å. Both Cu(1)-O(3) bond lengths are 2.20 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 Cu(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Cu(1) atom. In the third O site, O(3) is bonded to one Li(1), one V(1), one V(3), and one Cu(1) atom to form a mixture of distorted edge and corner-sharing OLiV2Cu trigonal pyramids. In the fourth O site, O(4) is bonded in a distorted 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 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 Li(2), one V(1), and one V(3) atom.