LiCu5(PO4)2 crystallizes in the monoclinic Pm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), and two equivalent O(7) atoms to form LiO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent Cu(2)O4 trigonal pyramids, and corners with two equivalent Cu(3)O4 trigonal pyramids. In the second Li site, Li(2) is bonded to one O(10), one O(11), and two equivalent O(5) atoms to form LiO4 tetrahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent Cu(5)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with four equivalent Cu(2)O4 trigonal pyramids. There are six inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(4), and two equivalent O(8) atoms to form distorted CuO4 trigonal pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, corners with four equivalent Cu(5)O4 tetrahedra, corners with two equivalent Cu(2)O4 trigonal pyramids, and corners with two equivalent Cu(3)O4 trigonal pyramids. In the second Cu site, Cu(2) is bonded to one O(11), one O(2), one O(5), and one O(8) atom to form distorted CuO4 trigonal pyramids that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Cu(5)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Cu(1)O4 trigonal pyramid, and corners with two equivalent Cu(2)O4 trigonal pyramids. In the third Cu site, Cu(3) is bonded to one O(4), one O(6), one O(7), and one O(9) atom to form distorted CuO4 trigonal pyramids that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Cu(5)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  a cornercorner with one Cu(1)O4 trigonal pyramid, and corners with two equivalent Cu(3)O4 trigonal pyramids. In the fourth Cu site, Cu(4) is bonded in a distorted rectangular see-saw-like geometry to one O(12), one O(3), one O(5), and one O(7) atom. In the fifth Cu site, Cu(5) is bonded to one O(1), one O(10), one O(6), and one O(8) atom to form CuO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent Cu(5)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Cu(2)O4 trigonal pyramid,  a cornercorner with one Cu(3)O4 trigonal pyramid, and corners with two equivalent Cu(1)O4 trigonal pyramids. In the sixth Cu site, Cu(6) is bonded in a distorted rectangular see-saw-like geometry to one O(12), one O(9), and two equivalent O(6) atoms. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), and two equivalent O(6) atoms to form PO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Cu(5)O4 tetrahedra,  a cornercorner with one Cu(1)O4 trigonal pyramid, and corners with four equivalent Cu(3)O4 trigonal pyramids. In the second P site, P(2) is bonded to one O(1), one O(2), and two equivalent O(5) atoms to form PO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Cu(5)O4 tetrahedra,  a cornercorner with one Cu(1)O4 trigonal pyramid, and corners with four equivalent Cu(2)O4 trigonal pyramids. In the third P site, P(3) is bonded to one O(11), one O(12), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Cu(2)O4 trigonal pyramids, and corners with two equivalent Cu(3)O4 trigonal pyramids. In the fourth P site, P(4) is bonded to one O(10), one O(9), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with four equivalent Cu(5)O4 tetrahedra, corners with two equivalent Cu(1)O4 trigonal pyramids, corners with two equivalent Cu(2)O4 trigonal pyramids, and corners with two equivalent Cu(3)O4 trigonal pyramids. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Cu(1), two equivalent Cu(5), and one P(2) atom to form distorted corner-sharing OCu3P tetrahedra. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Cu(2), and one P(2) atom. In the third O site, O(3) is bonded to one Li(1), two equivalent Cu(4), and one P(1) atom to form corner-sharing OLiCu2P tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Cu(1), two equivalent Cu(3), and one P(1) atom. In the fifth O site, O(5) is bonded to one Li(2), one Cu(2), one Cu(4), and one P(2) atom to form distorted OLiCu2P tetrahedra that share  a cornercorner with one O(1)Cu3P tetrahedra,  a cornercorner with one O(3)LiCu2P tetrahedra,  a cornercorner with one O(7)LiCu2P tetrahedra, corners with two equivalent O(11)LiCu2P tetrahedra, and corners with two equivalent O(5)LiCu2P tetrahedra. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Cu(3), one Cu(5), one Cu(6), and one P(1) atom. In the seventh O site, O(7) is bonded to one Li(1), one Cu(3), one Cu(4), and one P(3) atom to form distorted OLiCu2P tetrahedra that share  a cornercorner with one O(9)Cu3P tetrahedra,  a cornercorner with one O(11)LiCu2P tetrahedra,  a cornercorner with one O(5)LiCu2P tetrahedra, corners with two equivalent O(3)LiCu2P tetrahedra, and corners with two equivalent O(7)LiCu2P tetrahedra. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Cu(1), one Cu(2), one Cu(5), and one P(4) atom. In the ninth O site, O(9) is bonded to one Cu(6), two equivalent Cu(3), and one P(4) atom to form distorted corner-sharing OCu3P tetrahedra. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Cu(5), and one P(4) atom. In the eleventh O site, O(11) is bonded to one Li(2), two equivalent Cu(2), and one P(3) atom to form corner-sharing OLiCu2P tetrahedra. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Cu(6), two equivalent Cu(4), and one P(3) atom.
LiCu5(PO4)2 crystallizes in the monoclinic Pm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), and two equivalent O(7) atoms to form LiO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent Cu(2)O4 trigonal pyramids, and corners with two equivalent Cu(3)O4 trigonal pyramids. The Li(1)-O(2) bond length is 1.98 Å. The Li(1)-O(3) bond length is 1.98 Å. Both Li(1)-O(7) bond lengths are 2.02 Å. In the second Li site, Li(2) is bonded to one O(10), one O(11), and two equivalent O(5) atoms to form LiO4 tetrahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent Cu(5)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with four equivalent Cu(2)O4 trigonal pyramids. The Li(2)-O(10) bond length is 2.00 Å. The Li(2)-O(11) bond length is 1.99 Å. Both Li(2)-O(5) bond lengths are 2.05 Å. There are six inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(4), and two equivalent O(8) atoms to form distorted CuO4 trigonal pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, corners with four equivalent Cu(5)O4 tetrahedra, corners with two equivalent Cu(2)O4 trigonal pyramids, and corners with two equivalent Cu(3)O4 trigonal pyramids. The Cu(1)-O(1) bond length is 2.49 Å. The Cu(1)-O(4) bond length is 2.43 Å. Both Cu(1)-O(8) bond lengths are 1.93 Å. In the second Cu site, Cu(2) is bonded to one O(11), one O(2), one O(5), and one O(8) atom to form distorted CuO4 trigonal pyramids that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Cu(5)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Cu(1)O4 trigonal pyramid, and corners with two equivalent Cu(2)O4 trigonal pyramids. The Cu(2)-O(11) bond length is 2.28 Å. The Cu(2)-O(2) bond length is 2.07 Å. The Cu(2)-O(5) bond length is 2.01 Å. The Cu(2)-O(8) bond length is 2.26 Å. In the third Cu site, Cu(3) is bonded to one O(4), one O(6), one O(7), and one O(9) atom to form distorted CuO4 trigonal pyramids that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Cu(5)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  a cornercorner with one Cu(1)O4 trigonal pyramid, and corners with two equivalent Cu(3)O4 trigonal pyramids. The Cu(3)-O(4) bond length is 2.29 Å. The Cu(3)-O(6) bond length is 2.15 Å. The Cu(3)-O(7) bond length is 2.16 Å. The Cu(3)-O(9) bond length is 2.09 Å. In the fourth Cu site, Cu(4) is bonded in a distorted rectangular see-saw-like geometry to one O(12), one O(3), one O(5), and one O(7) atom. The Cu(4)-O(12) bond length is 2.05 Å. The Cu(4)-O(3) bond length is 2.25 Å. The Cu(4)-O(5) bond length is 2.30 Å. The Cu(4)-O(7) bond length is 2.00 Å. In the fifth Cu site, Cu(5) is bonded to one O(1), one O(10), one O(6), and one O(8) atom to form CuO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent Cu(5)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Cu(2)O4 trigonal pyramid,  a cornercorner with one Cu(3)O4 trigonal pyramid, and corners with two equivalent Cu(1)O4 trigonal pyramids. The Cu(5)-O(1) bond length is 2.19 Å. The Cu(5)-O(10) bond length is 2.21 Å. The Cu(5)-O(6) bond length is 2.12 Å. The Cu(5)-O(8) bond length is 2.06 Å. In the sixth Cu site, Cu(6) is bonded in a distorted rectangular see-saw-like geometry to one O(12), one O(9), and two equivalent O(6) atoms. The Cu(6)-O(12) bond length is 2.47 Å. The Cu(6)-O(9) bond length is 2.45 Å. Both Cu(6)-O(6) bond lengths are 1.93 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), and two equivalent O(6) atoms to form PO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Cu(5)O4 tetrahedra,  a cornercorner with one Cu(1)O4 trigonal pyramid, and corners with four equivalent Cu(3)O4 trigonal pyramids. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.54 Å. Both P(1)-O(6) bond lengths are 1.57 Å. In the second P site, P(2) is bonded to one O(1), one O(2), and two equivalent O(5) atoms to form PO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Cu(5)O4 tetrahedra,  a cornercorner with one Cu(1)O4 trigonal pyramid, and corners with four equivalent Cu(2)O4 trigonal pyramids. The P(2)-O(1) bond length is 1.55 Å. The P(2)-O(2) bond length is 1.57 Å. Both P(2)-O(5) bond lengths are 1.57 Å. In the third P site, P(3) is bonded to one O(11), one O(12), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Cu(2)O4 trigonal pyramids, and corners with two equivalent Cu(3)O4 trigonal pyramids. The P(3)-O(11) bond length is 1.55 Å. The P(3)-O(12) bond length is 1.55 Å. Both P(3)-O(7) bond lengths are 1.58 Å. In the fourth P site, P(4) is bonded to one O(10), one O(9), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with four equivalent Cu(5)O4 tetrahedra, corners with two equivalent Cu(1)O4 trigonal pyramids, corners with two equivalent Cu(2)O4 trigonal pyramids, and corners with two equivalent Cu(3)O4 trigonal pyramids. The P(4)-O(10) bond length is 1.55 Å. The P(4)-O(9) bond length is 1.55 Å. Both P(4)-O(8) bond lengths are 1.57 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Cu(1), two equivalent Cu(5), and one P(2) atom to form distorted corner-sharing OCu3P tetrahedra. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Cu(2), and one P(2) atom. In the third O site, O(3) is bonded to one Li(1), two equivalent Cu(4), and one P(1) atom to form corner-sharing OLiCu2P tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Cu(1), two equivalent Cu(3), and one P(1) atom. In the fifth O site, O(5) is bonded to one Li(2), one Cu(2), one Cu(4), and one P(2) atom to form distorted OLiCu2P tetrahedra that share  a cornercorner with one O(1)Cu3P tetrahedra,  a cornercorner with one O(3)LiCu2P tetrahedra,  a cornercorner with one O(7)LiCu2P tetrahedra, corners with two equivalent O(11)LiCu2P tetrahedra, and corners with two equivalent O(5)LiCu2P tetrahedra. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Cu(3), one Cu(5), one Cu(6), and one P(1) atom. In the seventh O site, O(7) is bonded to one Li(1), one Cu(3), one Cu(4), and one P(3) atom to form distorted OLiCu2P tetrahedra that share  a cornercorner with one O(9)Cu3P tetrahedra,  a cornercorner with one O(11)LiCu2P tetrahedra,  a cornercorner with one O(5)LiCu2P tetrahedra, corners with two equivalent O(3)LiCu2P tetrahedra, and corners with two equivalent O(7)LiCu2P tetrahedra. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Cu(1), one Cu(2), one Cu(5), and one P(4) atom. In the ninth O site, O(9) is bonded to one Cu(6), two equivalent Cu(3), and one P(4) atom to form distorted corner-sharing OCu3P tetrahedra. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Cu(5), and one P(4) atom. In the eleventh O site, O(11) is bonded to one Li(2), two equivalent Cu(2), and one P(3) atom to form corner-sharing OLiCu2P tetrahedra. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Cu(6), two equivalent Cu(4), and one P(3) atom.