Li4(CuO2)3 crystallizes in the monoclinic Cm space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Li(4)O4 trigonal pyramids,  an edgeedge with one Li(5)O5 square pyramid, and  an edgeedge with one Li(1)O5 trigonal bipyramid. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(2), one O(5), and two equivalent O(1) atoms. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), one O(5), and one O(7) atom. In the fourth Li site, Li(4) is bonded to one O(1), one O(3), one O(4), and one O(8) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent Li(1)O5 trigonal bipyramids,  a cornercorner with one Li(4)O4 trigonal pyramid, and  an edgeedge with one Li(5)O5 square pyramid. In the fifth Li site, Li(5) is bonded to one O(8), two equivalent O(4), and two equivalent O(7) atoms to form LiO5 square pyramids that share edges with two equivalent Li(1)O5 trigonal bipyramids and edges with two equivalent Li(4)O4 trigonal pyramids. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to one O(1), one O(2), one O(4), and one O(8) atom. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to one O(3), one O(5), one O(6), and one O(7) atom. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(4) atoms. In the fourth Cu site, Cu(4) is bonded in a rectangular see-saw-like geometry to two equivalent O(3) and two equivalent O(7) atoms. There are eight inequivalent O sites. In the first O site, O(5) is bonded to one Li(2), two equivalent Li(3), and two equivalent Cu(2) atoms to form a mixture of edge and corner-sharing OLi3Cu2 trigonal bipyramids. In the second O site, O(6) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Cu(2) atoms. In the third O site, O(7) is bonded to one Li(1), one Li(3), one Li(5), one Cu(2), and one Cu(4) atom to form a mixture of edge and corner-sharing OLi3Cu2 trigonal bipyramids. In the fourth O site, O(8) is bonded to one Li(5), two equivalent Li(4), and two equivalent Cu(1) atoms to form a mixture of edge and corner-sharing OLi3Cu2 trigonal bipyramids. In the fifth O site, O(1) is bonded to one Li(2), one Li(3), one Li(4), one Cu(1), and one Cu(3) atom to form a mixture of edge and corner-sharing OLi3Cu2 square pyramids. In the sixth O site, O(2) is bonded to one Li(2), two equivalent Li(1), and two equivalent Cu(1) atoms to form a mixture of distorted edge and corner-sharing OLi3Cu2 square pyramids. In the seventh O site, O(3) is bonded to one Li(1), one Li(3), one Li(4), one Cu(2), and one Cu(4) atom to form a mixture of edge and corner-sharing OLi3Cu2 trigonal bipyramids. In the eighth O site, O(4) is bonded to one Li(1), one Li(4), one Li(5), one Cu(1), and one Cu(3) atom to form a mixture of edge and corner-sharing OLi3Cu2 trigonal bipyramids.
Li4(CuO2)3 crystallizes in the monoclinic Cm space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Li(4)O4 trigonal pyramids,  an edgeedge with one Li(5)O5 square pyramid, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The Li(1)-O(2) bond length is 2.03 Å. The Li(1)-O(3) bond length is 2.12 Å. The Li(1)-O(4) bond length is 2.19 Å. The Li(1)-O(6) bond length is 2.01 Å. The Li(1)-O(7) bond length is 2.02 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(2), one O(5), and two equivalent O(1) atoms. The Li(2)-O(2) bond length is 1.89 Å. The Li(2)-O(5) bond length is 2.01 Å. Both Li(2)-O(1) bond lengths are 1.95 Å. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), one O(5), and one O(7) atom. The Li(3)-O(1) bond length is 1.90 Å. The Li(3)-O(3) bond length is 1.90 Å. The Li(3)-O(5) bond length is 1.98 Å. The Li(3)-O(7) bond length is 1.87 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(3), one O(4), and one O(8) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent Li(1)O5 trigonal bipyramids,  a cornercorner with one Li(4)O4 trigonal pyramid, and  an edgeedge with one Li(5)O5 square pyramid. The Li(4)-O(1) bond length is 1.97 Å. The Li(4)-O(3) bond length is 1.92 Å. The Li(4)-O(4) bond length is 1.92 Å. The Li(4)-O(8) bond length is 1.91 Å. In the fifth Li site, Li(5) is bonded to one O(8), two equivalent O(4), and two equivalent O(7) atoms to form LiO5 square pyramids that share edges with two equivalent Li(1)O5 trigonal bipyramids and edges with two equivalent Li(4)O4 trigonal pyramids. The Li(5)-O(8) bond length is 1.97 Å. Both Li(5)-O(4) bond lengths are 2.09 Å. Both Li(5)-O(7) bond lengths are 2.06 Å. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to one O(1), one O(2), one O(4), and one O(8) atom. The Cu(1)-O(1) bond length is 1.88 Å. The Cu(1)-O(2) bond length is 1.87 Å. The Cu(1)-O(4) bond length is 1.88 Å. The Cu(1)-O(8) bond length is 1.86 Å. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to one O(3), one O(5), one O(6), and one O(7) atom. The Cu(2)-O(3) bond length is 1.82 Å. The Cu(2)-O(5) bond length is 1.85 Å. The Cu(2)-O(6) bond length is 1.83 Å. The Cu(2)-O(7) bond length is 1.83 Å. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(4) atoms. Both Cu(3)-O(1) bond lengths are 1.85 Å. Both Cu(3)-O(4) bond lengths are 1.85 Å. In the fourth Cu site, Cu(4) is bonded in a rectangular see-saw-like geometry to two equivalent O(3) and two equivalent O(7) atoms. Both Cu(4)-O(3) bond lengths are 1.91 Å. Both Cu(4)-O(7) bond lengths are 1.93 Å. There are eight inequivalent O sites. In the first O site, O(5) is bonded to one Li(2), two equivalent Li(3), and two equivalent Cu(2) atoms to form a mixture of edge and corner-sharing OLi3Cu2 trigonal bipyramids. In the second O site, O(6) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Cu(2) atoms. In the third O site, O(7) is bonded to one Li(1), one Li(3), one Li(5), one Cu(2), and one Cu(4) atom to form a mixture of edge and corner-sharing OLi3Cu2 trigonal bipyramids. In the fourth O site, O(8) is bonded to one Li(5), two equivalent Li(4), and two equivalent Cu(1) atoms to form a mixture of edge and corner-sharing OLi3Cu2 trigonal bipyramids. In the fifth O site, O(1) is bonded to one Li(2), one Li(3), one Li(4), one Cu(1), and one Cu(3) atom to form a mixture of edge and corner-sharing OLi3Cu2 square pyramids. In the sixth O site, O(2) is bonded to one Li(2), two equivalent Li(1), and two equivalent Cu(1) atoms to form a mixture of distorted edge and corner-sharing OLi3Cu2 square pyramids. In the seventh O site, O(3) is bonded to one Li(1), one Li(3), one Li(4), one Cu(2), and one Cu(4) atom to form a mixture of edge and corner-sharing OLi3Cu2 trigonal bipyramids. In the eighth O site, O(4) is bonded to one Li(1), one Li(4), one Li(5), one Cu(1), and one Cu(3) atom to form a mixture of edge and corner-sharing OLi3Cu2 trigonal bipyramids.