Li2V3CuO8 is Spinel-derived structured and crystallizes in the trigonal R3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-65°. In the second Li site, Li(2) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Cu(1)O4 tetrahedra, and edges with six equivalent V(1)O6 octahedra. V(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Cu(1)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. Cu(1) is bonded to one O(4) and three equivalent O(3) atoms to form CuO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-65°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1) and three equivalent V(1) atoms. In the second O site, O(2) is bonded to one Li(1), one Li(2), and two equivalent V(1) atoms to form distorted OLi2V2 trigonal pyramids that share corners with two equivalent O(2)Li2V2 trigonal pyramids, corners with two equivalent O(4)V3Cu trigonal pyramids, corners with seven equivalent O(3)LiV2Cu trigonal pyramids, and edges with two equivalent O(2)Li2V2 trigonal pyramids. In the third O site, O(3) is bonded to one Li(2), two equivalent V(1), and one Cu(1) atom to form distorted OLiV2Cu trigonal pyramids that share  a cornercorner with one O(4)V3Cu trigonal pyramid, corners with two equivalent O(3)LiV2Cu trigonal pyramids, corners with seven equivalent O(2)Li2V2 trigonal pyramids,  an edgeedge with one O(4)V3Cu trigonal pyramid, and edges with two equivalent O(3)LiV2Cu trigonal pyramids. In the fourth O site, O(4) is bonded to three equivalent V(1) and one Cu(1) atom to form distorted OV3Cu trigonal pyramids that share corners with three equivalent O(3)LiV2Cu trigonal pyramids, corners with six equivalent O(2)Li2V2 trigonal pyramids, and edges with three equivalent O(3)LiV2Cu trigonal pyramids.
Li2V3CuO8 is Spinel-derived structured and crystallizes in the trigonal R3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-65°. The Li(1)-O(1) bond length is 2.01 Å. All Li(1)-O(2) bond lengths are 1.98 Å. In the second Li site, Li(2) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Cu(1)O4 tetrahedra, and edges with six equivalent V(1)O6 octahedra. All Li(2)-O(2) bond lengths are 2.11 Å. All Li(2)-O(3) bond lengths are 2.10 Å. V(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Cu(1)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(4) bond length is 2.03 Å. Both V(1)-O(2) bond lengths are 1.91 Å. Both V(1)-O(3) bond lengths are 1.95 Å. Cu(1) is bonded to one O(4) and three equivalent O(3) atoms to form CuO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-65°. The Cu(1)-O(4) bond length is 1.97 Å. All Cu(1)-O(3) bond lengths are 1.99 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1) and three equivalent V(1) atoms. In the second O site, O(2) is bonded to one Li(1), one Li(2), and two equivalent V(1) atoms to form distorted OLi2V2 trigonal pyramids that share corners with two equivalent O(2)Li2V2 trigonal pyramids, corners with two equivalent O(4)V3Cu trigonal pyramids, corners with seven equivalent O(3)LiV2Cu trigonal pyramids, and edges with two equivalent O(2)Li2V2 trigonal pyramids. In the third O site, O(3) is bonded to one Li(2), two equivalent V(1), and one Cu(1) atom to form distorted OLiV2Cu trigonal pyramids that share  a cornercorner with one O(4)V3Cu trigonal pyramid, corners with two equivalent O(3)LiV2Cu trigonal pyramids, corners with seven equivalent O(2)Li2V2 trigonal pyramids,  an edgeedge with one O(4)V3Cu trigonal pyramid, and edges with two equivalent O(3)LiV2Cu trigonal pyramids. In the fourth O site, O(4) is bonded to three equivalent V(1) and one Cu(1) atom to form distorted OV3Cu trigonal pyramids that share corners with three equivalent O(3)LiV2Cu trigonal pyramids, corners with six equivalent O(2)Li2V2 trigonal pyramids, and edges with three equivalent O(3)LiV2Cu trigonal pyramids.