Li3Cu5O8 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Cu(3)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, edges with two equivalent Cu(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cu(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-4°. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to six equivalent O(2) atoms to form CuO6 octahedra that share corners with six equivalent Cu(2)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and edges with six equivalent Cu(3)O6 octahedra. The corner-sharing octahedral tilt angles are 4°. In the second Cu site, Cu(2) is bonded to six equivalent O(2) atoms to form CuO6 octahedra that share corners with six equivalent Cu(1)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and edges with six equivalent Cu(3)O6 octahedra. The corner-sharing octahedral tilt angles are 4°. In the third Cu site, Cu(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CuO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, edges with two equivalent Cu(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cu(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-4°. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(1) and three equivalent Cu(3) atoms to form OLi3Cu3 octahedra that share corners with six equivalent O(1)Li3Cu3 octahedra and edges with twelve equivalent O(2)Li2Cu4 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to two equivalent Li(1), one Cu(1), one Cu(2), and two equivalent Cu(3) atoms to form OLi2Cu4 octahedra that share corners with six equivalent O(2)Li2Cu4 octahedra, edges with four equivalent O(1)Li3Cu3 octahedra, and edges with eight equivalent O(2)Li2Cu4 octahedra. The corner-sharing octahedra are not tilted.
Li3Cu5O8 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Cu(3)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, edges with two equivalent Cu(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cu(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-4°. Both Li(1)-O(1) bond lengths are 2.14 Å. All Li(1)-O(2) bond lengths are 2.13 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to six equivalent O(2) atoms to form CuO6 octahedra that share corners with six equivalent Cu(2)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and edges with six equivalent Cu(3)O6 octahedra. The corner-sharing octahedral tilt angles are 4°. All Cu(1)-O(2) bond lengths are 2.08 Å. In the second Cu site, Cu(2) is bonded to six equivalent O(2) atoms to form CuO6 octahedra that share corners with six equivalent Cu(1)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and edges with six equivalent Cu(3)O6 octahedra. The corner-sharing octahedral tilt angles are 4°. All Cu(2)-O(2) bond lengths are 2.08 Å. In the third Cu site, Cu(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CuO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, edges with two equivalent Cu(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Cu(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-4°. Both Cu(3)-O(1) bond lengths are 2.02 Å. All Cu(3)-O(2) bond lengths are 2.03 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(1) and three equivalent Cu(3) atoms to form OLi3Cu3 octahedra that share corners with six equivalent O(1)Li3Cu3 octahedra and edges with twelve equivalent O(2)Li2Cu4 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to two equivalent Li(1), one Cu(1), one Cu(2), and two equivalent Cu(3) atoms to form OLi2Cu4 octahedra that share corners with six equivalent O(2)Li2Cu4 octahedra, edges with four equivalent O(1)Li3Cu3 octahedra, and edges with eight equivalent O(2)Li2Cu4 octahedra. The corner-sharing octahedra are not tilted.