LiCu5(PO4)2 crystallizes in the monoclinic Pm space group. Li(1) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form LiO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with four equivalent Cu(1)O4 tetrahedra. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form distorted CuO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Cu(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. In the second Cu site, Cu(2) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), one O(4), and one O(6) atom. In the third Cu site, Cu(3) is bonded in a 3-coordinate geometry to one O(6) and two equivalent O(3) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra and corners with four equivalent Cu(1)O4 tetrahedra. In the second P site, P(2) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra and corners with four equivalent Cu(1)O4 tetrahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Cu(1), and one P(1) atom. In the second O site, O(2) is bonded to one Li(1), two equivalent Cu(2), and one P(1) atom to form distorted corner-sharing OLiCu2P tetrahedra. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Cu(1), one Cu(2), one Cu(3), and one P(1) atom. In the fourth O site, O(4) is bonded to one Li(1), one Cu(1), one Cu(2), and one P(2) atom to form distorted corner-sharing OLiCu2P tetrahedra. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Cu(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Cu(3), two equivalent Cu(2), and one P(2) atom.
LiCu5(PO4)2 crystallizes in the monoclinic Pm space group. Li(1) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form LiO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with four equivalent Cu(1)O4 tetrahedra. The Li(1)-O(1) bond length is 2.00 Å. The Li(1)-O(2) bond length is 1.96 Å. Both Li(1)-O(4) bond lengths are 2.03 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form distorted CuO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Cu(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Cu(1)-O(1) bond length is 2.30 Å. The Cu(1)-O(3) bond length is 2.12 Å. The Cu(1)-O(4) bond length is 2.11 Å. The Cu(1)-O(5) bond length is 2.11 Å. In the second Cu site, Cu(2) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), one O(4), and one O(6) atom. The Cu(2)-O(2) bond length is 2.33 Å. The Cu(2)-O(3) bond length is 2.29 Å. The Cu(2)-O(4) bond length is 2.00 Å. The Cu(2)-O(6) bond length is 2.03 Å. In the third Cu site, Cu(3) is bonded in a 3-coordinate geometry to one O(6) and two equivalent O(3) atoms. The Cu(3)-O(6) bond length is 2.40 Å. Both Cu(3)-O(3) bond lengths are 1.94 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra and corners with four equivalent Cu(1)O4 tetrahedra. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.55 Å. Both P(1)-O(3) bond lengths are 1.58 Å. In the second P site, P(2) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra and corners with four equivalent Cu(1)O4 tetrahedra. The P(2)-O(5) bond length is 1.54 Å. The P(2)-O(6) bond length is 1.55 Å. Both P(2)-O(4) bond lengths are 1.58 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Cu(1), and one P(1) atom. In the second O site, O(2) is bonded to one Li(1), two equivalent Cu(2), and one P(1) atom to form distorted corner-sharing OLiCu2P tetrahedra. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Cu(1), one Cu(2), one Cu(3), and one P(1) atom. In the fourth O site, O(4) is bonded to one Li(1), one Cu(1), one Cu(2), and one P(2) atom to form distorted corner-sharing OLiCu2P tetrahedra. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Cu(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Cu(3), two equivalent Cu(2), and one P(2) atom.