Li5Cu(PO4)2 crystallizes in the monoclinic Pc space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Cu(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. In the second Li site, Li(2) is bonded to one O(3), one O(4), one O(6), and one O(8) atom to form LiO4 tetrahedra that share corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent Cu(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(4)O4 tetrahedra. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(5), and one O(7) atom to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra, and  an edgeedge with one Cu(1)O4 tetrahedra. In the fourth Li site, Li(4) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. In the fifth Li site, Li(5) is bonded to one O(1), one O(6), one O(7), and one O(8) atom to form LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Cu(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. Cu(1) is bonded to one O(1), one O(2), one O(3), and one O(8) atom to form CuO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, and corners with two equivalent Cu(1)O4 tetrahedra. In the second P site, P(2) is bonded to one O(2), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, and corners with two equivalent Cu(1)O4 tetrahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Li(5), one Cu(1), and one P(1) atom to form distorted OLi2CuP trigonal pyramids that share corners with two equivalent O(3)Li2CuP tetrahedra, corners with two equivalent O(8)Li2CuP tetrahedra, corners with two equivalent O(5)Li3P tetrahedra, corners with two equivalent O(6)Li3P tetrahedra,  an edgeedge with one O(7)Li3P tetrahedra, and  an edgeedge with one O(2)Li2CuP trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Cu(1), and one P(2) atom to form distorted OLi2CuP trigonal pyramids that share corners with two equivalent O(3)Li2CuP tetrahedra, corners with two equivalent O(8)Li2CuP tetrahedra, corners with two equivalent O(5)Li3P tetrahedra, corners with two equivalent O(7)Li3P tetrahedra, corners with two equivalent O(4)Li3P trigonal pyramids, and  an edgeedge with one O(1)Li2CuP trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Cu(1), and one P(1) atom to form distorted OLi2CuP tetrahedra that share corners with two equivalent O(8)Li2CuP tetrahedra, corners with two equivalent O(5)Li3P tetrahedra, corners with two equivalent O(6)Li3P tetrahedra, corners with two equivalent O(1)Li2CuP trigonal pyramids, corners with two equivalent O(2)Li2CuP trigonal pyramids, and  an edgeedge with one O(4)Li3P trigonal pyramid. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(4), and one P(2) atom to form distorted OLi3P trigonal pyramids that share corners with two equivalent O(8)Li2CuP tetrahedra, corners with two equivalent O(5)Li3P tetrahedra, corners with two equivalent O(7)Li3P tetrahedra, corners with two equivalent O(2)Li2CuP trigonal pyramids,  an edgeedge with one O(3)Li2CuP tetrahedra, and  an edgeedge with one O(6)Li3P tetrahedra. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(4), and one P(1) atom to form distorted OLi3P tetrahedra that share corners with two equivalent O(3)Li2CuP tetrahedra, corners with two equivalent O(6)Li3P tetrahedra, corners with two equivalent O(7)Li3P tetrahedra, corners with two equivalent O(1)Li2CuP trigonal pyramids, corners with two equivalent O(2)Li2CuP trigonal pyramids, and corners with two equivalent O(4)Li3P trigonal pyramids. In the sixth O site, O(6) is bonded to one Li(2), one Li(4), one Li(5), and one P(1) atom to form distorted OLi3P tetrahedra that share corners with two equivalent O(3)Li2CuP tetrahedra, corners with two equivalent O(8)Li2CuP tetrahedra, corners with two equivalent O(5)Li3P tetrahedra, corners with two equivalent O(7)Li3P tetrahedra, corners with two equivalent O(1)Li2CuP trigonal pyramids, and  an edgeedge with one O(4)Li3P trigonal pyramid. In the seventh O site, O(7) is bonded to one Li(3), one Li(4), one Li(5), and one P(2) atom to form distorted OLi3P tetrahedra that share corners with two equivalent O(8)Li2CuP tetrahedra, corners with two equivalent O(5)Li3P tetrahedra, corners with two equivalent O(6)Li3P tetrahedra, corners with two equivalent O(2)Li2CuP trigonal pyramids, corners with two equivalent O(4)Li3P trigonal pyramids, and  an edgeedge with one O(1)Li2CuP trigonal pyramid. In the eighth O site, O(8) is bonded to one Li(2), one Li(5), one Cu(1), and one P(2) atom to form distorted OLi2CuP tetrahedra that share corners with two equivalent O(3)Li2CuP tetrahedra, corners with two equivalent O(6)Li3P tetrahedra, corners with two equivalent O(7)Li3P tetrahedra, corners with two equivalent O(1)Li2CuP trigonal pyramids, corners with two equivalent O(2)Li2CuP trigonal pyramids, and corners with two equivalent O(4)Li3P trigonal pyramids.
Li5Cu(PO4)2 crystallizes in the monoclinic Pc space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Cu(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The Li(1)-O(2) bond length is 2.00 Å. The Li(1)-O(3) bond length is 2.03 Å. The Li(1)-O(4) bond length is 1.99 Å. The Li(1)-O(5) bond length is 1.99 Å. In the second Li site, Li(2) is bonded to one O(3), one O(4), one O(6), and one O(8) atom to form LiO4 tetrahedra that share corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent Cu(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(4)O4 tetrahedra. The Li(2)-O(3) bond length is 1.99 Å. The Li(2)-O(4) bond length is 2.03 Å. The Li(2)-O(6) bond length is 2.03 Å. The Li(2)-O(8) bond length is 1.94 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(5), and one O(7) atom to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(5)O4 tetrahedra, and  an edgeedge with one Cu(1)O4 tetrahedra. The Li(3)-O(1) bond length is 2.05 Å. The Li(3)-O(2) bond length is 2.01 Å. The Li(3)-O(5) bond length is 1.99 Å. The Li(3)-O(7) bond length is 2.03 Å. In the fourth Li site, Li(4) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The Li(4)-O(4) bond length is 1.99 Å. The Li(4)-O(5) bond length is 1.98 Å. The Li(4)-O(6) bond length is 2.05 Å. The Li(4)-O(7) bond length is 1.98 Å. In the fifth Li site, Li(5) is bonded to one O(1), one O(6), one O(7), and one O(8) atom to form LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Cu(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The Li(5)-O(1) bond length is 1.96 Å. The Li(5)-O(6) bond length is 1.97 Å. The Li(5)-O(7) bond length is 2.03 Å. The Li(5)-O(8) bond length is 1.96 Å. Cu(1) is bonded to one O(1), one O(2), one O(3), and one O(8) atom to form CuO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The Cu(1)-O(1) bond length is 2.14 Å. The Cu(1)-O(2) bond length is 2.17 Å. The Cu(1)-O(3) bond length is 2.00 Å. The Cu(1)-O(8) bond length is 2.08 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, and corners with two equivalent Cu(1)O4 tetrahedra. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(2), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, and corners with two equivalent Cu(1)O4 tetrahedra. The P(2)-O(2) bond length is 1.57 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.56 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Li(5), one Cu(1), and one P(1) atom to form distorted OLi2CuP trigonal pyramids that share corners with two equivalent O(3)Li2CuP tetrahedra, corners with two equivalent O(8)Li2CuP tetrahedra, corners with two equivalent O(5)Li3P tetrahedra, corners with two equivalent O(6)Li3P tetrahedra,  an edgeedge with one O(7)Li3P tetrahedra, and  an edgeedge with one O(2)Li2CuP trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Cu(1), and one P(2) atom to form distorted OLi2CuP trigonal pyramids that share corners with two equivalent O(3)Li2CuP tetrahedra, corners with two equivalent O(8)Li2CuP tetrahedra, corners with two equivalent O(5)Li3P tetrahedra, corners with two equivalent O(7)Li3P tetrahedra, corners with two equivalent O(4)Li3P trigonal pyramids, and  an edgeedge with one O(1)Li2CuP trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Cu(1), and one P(1) atom to form distorted OLi2CuP tetrahedra that share corners with two equivalent O(8)Li2CuP tetrahedra, corners with two equivalent O(5)Li3P tetrahedra, corners with two equivalent O(6)Li3P tetrahedra, corners with two equivalent O(1)Li2CuP trigonal pyramids, corners with two equivalent O(2)Li2CuP trigonal pyramids, and  an edgeedge with one O(4)Li3P trigonal pyramid. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(4), and one P(2) atom to form distorted OLi3P trigonal pyramids that share corners with two equivalent O(8)Li2CuP tetrahedra, corners with two equivalent O(5)Li3P tetrahedra, corners with two equivalent O(7)Li3P tetrahedra, corners with two equivalent O(2)Li2CuP trigonal pyramids,  an edgeedge with one O(3)Li2CuP tetrahedra, and  an edgeedge with one O(6)Li3P tetrahedra. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(4), and one P(1) atom to form distorted OLi3P tetrahedra that share corners with two equivalent O(3)Li2CuP tetrahedra, corners with two equivalent O(6)Li3P tetrahedra, corners with two equivalent O(7)Li3P tetrahedra, corners with two equivalent O(1)Li2CuP trigonal pyramids, corners with two equivalent O(2)Li2CuP trigonal pyramids, and corners with two equivalent O(4)Li3P trigonal pyramids. In the sixth O site, O(6) is bonded to one Li(2), one Li(4), one Li(5), and one P(1) atom to form distorted OLi3P tetrahedra that share corners with two equivalent O(3)Li2CuP tetrahedra, corners with two equivalent O(8)Li2CuP tetrahedra, corners with two equivalent O(5)Li3P tetrahedra, corners with two equivalent O(7)Li3P tetrahedra, corners with two equivalent O(1)Li2CuP trigonal pyramids, and  an edgeedge with one O(4)Li3P trigonal pyramid. In the seventh O site, O(7) is bonded to one Li(3), one Li(4), one Li(5), and one P(2) atom to form distorted OLi3P tetrahedra that share corners with two equivalent O(8)Li2CuP tetrahedra, corners with two equivalent O(5)Li3P tetrahedra, corners with two equivalent O(6)Li3P tetrahedra, corners with two equivalent O(2)Li2CuP trigonal pyramids, corners with two equivalent O(4)Li3P trigonal pyramids, and  an edgeedge with one O(1)Li2CuP trigonal pyramid. In the eighth O site, O(8) is bonded to one Li(2), one Li(5), one Cu(1), and one P(2) atom to form distorted OLi2CuP tetrahedra that share corners with two equivalent O(3)Li2CuP tetrahedra, corners with two equivalent O(6)Li3P tetrahedra, corners with two equivalent O(7)Li3P tetrahedra, corners with two equivalent O(1)Li2CuP trigonal pyramids, corners with two equivalent O(2)Li2CuP trigonal pyramids, and corners with two equivalent O(4)Li3P trigonal pyramids.