Li7(CuO2)6 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Li(4)O4 trigonal pyramid,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 39°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Li(1)O4 tetrahedra. In the third Li site, Li(3) is bonded to one O(1), one O(3), one O(4), one O(6), and two equivalent O(5) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Li(4)O4 trigonal pyramid,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra, and edges with two equivalent Li(4)O4 trigonal pyramids. In the fourth Li site, Li(4) is bonded to one O(4), one O(5), and two equivalent O(6) atoms to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, edges with two equivalent Li(3)O6 octahedra, and  an edgeedge with one Li(4)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 40°. There are three 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(3), and one O(6) atom. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to one O(1), one O(2), one O(4), and one O(5) atom. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to one O(3), one O(4), one O(5), and one O(6) atom. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Cu(1), and one Cu(2) atom to form a mixture of corner and edge-sharing OLi3Cu2 square pyramids. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one Cu(1), and one Cu(2) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Cu(1), and one Cu(3) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Li(4), one Cu(2), and one Cu(3) atom to form a mixture of distorted corner and edge-sharing OLi3Cu2 trigonal bipyramids. In the fifth O site, O(5) is bonded to one Li(4), two equivalent Li(3), one Cu(2), and one Cu(3) atom to form a mixture of corner and edge-sharing OLi3Cu2 trigonal bipyramids. In the sixth O site, O(6) is bonded to one Li(3), two equivalent Li(4), one Cu(1), and one Cu(3) atom to form a mixture of distorted corner and edge-sharing OLi3Cu2 square pyramids.
Li7(CuO2)6 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Li(4)O4 trigonal pyramid,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 39°. The Li(1)-O(1) bond length is 1.94 Å. The Li(1)-O(4) bond length is 2.00 Å. Both Li(1)-O(2) bond lengths are 1.97 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Li(1)O4 tetrahedra. Both Li(2)-O(1) bond lengths are 2.10 Å. Both Li(2)-O(2) bond lengths are 2.59 Å. Both Li(2)-O(3) bond lengths are 2.08 Å. In the third Li site, Li(3) is bonded to one O(1), one O(3), one O(4), one O(6), and two equivalent O(5) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Li(4)O4 trigonal pyramid,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra, and edges with two equivalent Li(4)O4 trigonal pyramids. The Li(3)-O(1) bond length is 2.11 Å. The Li(3)-O(3) bond length is 2.05 Å. The Li(3)-O(4) bond length is 2.49 Å. The Li(3)-O(6) bond length is 2.49 Å. There is one shorter (2.07 Å) and one longer (2.14 Å) Li(3)-O(5) bond length. In the fourth Li site, Li(4) is bonded to one O(4), one O(5), and two equivalent O(6) atoms to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, edges with two equivalent Li(3)O6 octahedra, and  an edgeedge with one Li(4)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 40°. The Li(4)-O(4) bond length is 1.99 Å. The Li(4)-O(5) bond length is 1.94 Å. There is one shorter (1.97 Å) and one longer (1.98 Å) Li(4)-O(6) bond length. There are three 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(3), and one O(6) atom. The Cu(1)-O(1) bond length is 1.89 Å. The Cu(1)-O(2) bond length is 1.88 Å. The Cu(1)-O(3) bond length is 1.86 Å. The Cu(1)-O(6) bond length is 1.88 Å. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to one O(1), one O(2), one O(4), and one O(5) atom. The Cu(2)-O(1) bond length is 1.88 Å. The Cu(2)-O(2) bond length is 1.86 Å. The Cu(2)-O(4) bond length is 1.86 Å. The Cu(2)-O(5) bond length is 1.87 Å. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to one O(3), one O(4), one O(5), and one O(6) atom. The Cu(3)-O(3) bond length is 1.86 Å. The Cu(3)-O(4) bond length is 1.87 Å. The Cu(3)-O(5) bond length is 1.88 Å. The Cu(3)-O(6) bond length is 1.86 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Cu(1), and one Cu(2) atom to form a mixture of corner and edge-sharing OLi3Cu2 square pyramids. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one Cu(1), and one Cu(2) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Cu(1), and one Cu(3) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Li(4), one Cu(2), and one Cu(3) atom to form a mixture of distorted corner and edge-sharing OLi3Cu2 trigonal bipyramids. In the fifth O site, O(5) is bonded to one Li(4), two equivalent Li(3), one Cu(2), and one Cu(3) atom to form a mixture of corner and edge-sharing OLi3Cu2 trigonal bipyramids. In the sixth O site, O(6) is bonded to one Li(3), two equivalent Li(4), one Cu(1), and one Cu(3) atom to form a mixture of distorted corner and edge-sharing OLi3Cu2 square pyramids.