Li2V4CrCuO12 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form distorted LiO6 pentagonal pyramids that share corners with four equivalent V(2)O4 tetrahedra, edges with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Cu(1)O6 pentagonal pyramid, and edges with two equivalent V(1)O5 trigonal bipyramids. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(4) 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), one O(5), and one O(6) atom to form VO5 trigonal bipyramids that share corners with two equivalent Cr(1)O6 octahedra, corners with three equivalent V(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 pentagonal pyramid, and  an edgeedge with one Cu(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 30-50°. 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 Cr(1)O6 octahedra, corners with two equivalent Li(1)O6 pentagonal pyramids, corners with two equivalent Cu(1)O6 pentagonal pyramids, and corners with three equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 63°. Cr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Li(1)O6 pentagonal pyramids, and edges with two equivalent Cu(1)O6 pentagonal pyramids. Cu(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form distorted CuO6 pentagonal pyramids that share corners with four equivalent V(2)O4 tetrahedra, edges with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(1)O6 pentagonal pyramid, and edges with two equivalent V(1)O5 trigonal bipyramids. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one V(1), one Cr(1), and one Cu(1) atom to form a mixture of distorted corner and edge-sharing OLiVCrCu trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one Cr(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one V(2), one Cr(1), and one Cu(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate 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 V(1), one V(2), and one Cu(1) atom.
Li2V4CrCuO12 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form distorted LiO6 pentagonal pyramids that share corners with four equivalent V(2)O4 tetrahedra, edges with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Cu(1)O6 pentagonal pyramid, and edges with two equivalent V(1)O5 trigonal bipyramids. Both Li(1)-O(2) bond lengths are 2.30 Å. Both Li(1)-O(3) bond lengths are 2.17 Å. Both Li(1)-O(5) bond lengths are 2.40 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(4) atoms. Both Li(2)-O(1) bond lengths are 2.05 Å. Both Li(2)-O(4) bond lengths are 2.07 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), one O(5), and one O(6) atom to form VO5 trigonal bipyramids that share corners with two equivalent Cr(1)O6 octahedra, corners with three equivalent V(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 pentagonal pyramid, and  an edgeedge with one Cu(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 30-50°. The V(1)-O(1) bond length is 1.83 Å. The V(1)-O(2) bond length is 1.74 Å. The V(1)-O(4) bond length is 1.96 Å. The V(1)-O(5) bond length is 1.99 Å. The V(1)-O(6) bond length is 2.17 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 Cr(1)O6 octahedra, corners with two equivalent Li(1)O6 pentagonal pyramids, corners with two equivalent Cu(1)O6 pentagonal pyramids, and corners with three equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 63°. The V(2)-O(3) bond length is 1.75 Å. The V(2)-O(4) bond length is 1.78 Å. The V(2)-O(5) bond length is 1.74 Å. The V(2)-O(6) bond length is 1.74 Å. Cr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Li(1)O6 pentagonal pyramids, and edges with two equivalent Cu(1)O6 pentagonal pyramids. Both Cr(1)-O(1) bond lengths are 2.01 Å. Both Cr(1)-O(2) bond lengths are 1.99 Å. Both Cr(1)-O(3) bond lengths are 2.02 Å. Cu(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form distorted CuO6 pentagonal pyramids that share corners with four equivalent V(2)O4 tetrahedra, edges with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(1)O6 pentagonal pyramid, and edges with two equivalent V(1)O5 trigonal bipyramids. Both Cu(1)-O(1) bond lengths are 2.19 Å. Both Cu(1)-O(3) bond lengths are 2.28 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 to one Li(2), one V(1), one Cr(1), and one Cu(1) atom to form a mixture of distorted corner and edge-sharing OLiVCrCu trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one Cr(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one V(2), one Cr(1), and one Cu(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate 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 V(1), one V(2), and one Cu(1) atom.