LiCu2O2 crystallizes in the tetragonal P4_2/nmc space group. Li(1) is bonded to two equivalent O(1) and three equivalent O(2) atoms to form LiO5 square pyramids that share corners with four equivalent Cu(2)O5 square pyramids, edges with four equivalent Li(1)O5 square pyramids, and edges with four equivalent Cu(2)O5 square pyramids. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a linear geometry to one O(1) and one O(2) atom. In the second Cu site, Cu(2) is bonded to two equivalent O(2) and three equivalent O(1) atoms to form distorted CuO5 square pyramids that share corners with four equivalent Li(1)O5 square pyramids, edges with four equivalent Li(1)O5 square pyramids, and edges with four equivalent Cu(2)O5 square pyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Cu(1), and three equivalent Cu(2) atoms to form distorted OLi2Cu4 octahedra that share corners with five equivalent O(2)Li3Cu3 octahedra, edges with four equivalent O(1)Li2Cu4 octahedra, and edges with four equivalent O(2)Li3Cu3 octahedra. The corner-sharing octahedral tilt angles range from 1-19°. In the second O site, O(2) is bonded to three equivalent Li(1), one Cu(1), and two equivalent Cu(2) atoms to form OLi3Cu3 octahedra that share corners with five equivalent O(1)Li2Cu4 octahedra, edges with four equivalent O(1)Li2Cu4 octahedra, and edges with four equivalent O(2)Li3Cu3 octahedra. The corner-sharing octahedral tilt angles range from 1-19°.
LiCu2O2 crystallizes in the tetragonal P4_2/nmc space group. Li(1) is bonded to two equivalent O(1) and three equivalent O(2) atoms to form LiO5 square pyramids that share corners with four equivalent Cu(2)O5 square pyramids, edges with four equivalent Li(1)O5 square pyramids, and edges with four equivalent Cu(2)O5 square pyramids. Both Li(1)-O(1) bond lengths are 2.07 Å. There is one shorter (2.04 Å) and two longer (2.08 Å) Li(1)-O(2) bond lengths. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a linear geometry to one O(1) and one O(2) atom. The Cu(1)-O(1) bond length is 1.85 Å. The Cu(1)-O(2) bond length is 1.86 Å. In the second Cu site, Cu(2) is bonded to two equivalent O(2) and three equivalent O(1) atoms to form distorted CuO5 square pyramids that share corners with four equivalent Li(1)O5 square pyramids, edges with four equivalent Li(1)O5 square pyramids, and edges with four equivalent Cu(2)O5 square pyramids. Both Cu(2)-O(2) bond lengths are 1.98 Å. There are two shorter (1.96 Å) and one longer (2.52 Å) Cu(2)-O(1) bond length. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Cu(1), and three equivalent Cu(2) atoms to form distorted OLi2Cu4 octahedra that share corners with five equivalent O(2)Li3Cu3 octahedra, edges with four equivalent O(1)Li2Cu4 octahedra, and edges with four equivalent O(2)Li3Cu3 octahedra. The corner-sharing octahedral tilt angles range from 1-19°. In the second O site, O(2) is bonded to three equivalent Li(1), one Cu(1), and two equivalent Cu(2) atoms to form OLi3Cu3 octahedra that share corners with five equivalent O(1)Li2Cu4 octahedra, edges with four equivalent O(1)Li2Cu4 octahedra, and edges with four equivalent O(2)Li3Cu3 octahedra. The corner-sharing octahedral tilt angles range from 1-19°.