Li3Cu3(PO4)2 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), and one O(7) atom to form LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Cu(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent Cu(2)O4 trigonal pyramids. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), and one O(5) 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 Cu(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent Cu(1)O4 trigonal pyramids. In the third Li site, Li(3) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Cu(1)O4 trigonal pyramids, and corners with two equivalent Cu(2)O4 trigonal pyramids. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(3), one O(5), one O(6), and one O(8) atom to form distorted CuO4 trigonal pyramids that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Cu(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent Cu(2)O4 trigonal pyramids. In the second Cu site, Cu(2) is bonded to one O(2), one O(6), one O(7), and one O(8) atom to form distorted CuO4 trigonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Cu(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent Cu(1)O4 trigonal pyramids. In the third Cu site, Cu(3) is bonded to one O(1), one O(5), one O(7), and one O(8) atom to form distorted CuO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Cu(1)O4 trigonal pyramids, and corners with two equivalent Cu(2)O4 trigonal pyramids. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), 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 Cu(3)O4 tetrahedra, corners with two equivalent Cu(1)O4 trigonal pyramids, and corners with two equivalent Cu(2)O4 trigonal pyramids. In the second P site, P(2) is bonded to one O(4), one O(5), one O(6), and one O(7) 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 Cu(3)O4 tetrahedra, corners with two equivalent Cu(1)O4 trigonal pyramids, and corners with two equivalent Cu(2)O4 trigonal pyramids. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Cu(3), and one P(1) atom to form distorted OLi2CuP tetrahedra that share corners with two equivalent O(2)Li2CuP tetrahedra, corners with two equivalent O(3)Li2CuP tetrahedra, corners with two equivalent O(4)Li3P tetrahedra, and corners with two equivalent O(7)LiCu2P tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Cu(2), and one P(1) atom to form distorted OLi2CuP tetrahedra that share corners with two equivalent O(1)Li2CuP tetrahedra, corners with two equivalent O(3)Li2CuP tetrahedra, corners with two equivalent O(4)Li3P tetrahedra, and corners with two equivalent O(7)LiCu2P tetrahedra. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Cu(1), and one P(1) atom to form distorted OLi2CuP tetrahedra that share corners with two equivalent O(1)Li2CuP tetrahedra, corners with two equivalent O(2)Li2CuP tetrahedra, and corners with two equivalent O(4)Li3P tetrahedra. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), and one P(2) atom to form OLi3P tetrahedra that share corners with two equivalent O(1)Li2CuP tetrahedra, corners with two equivalent O(2)Li2CuP tetrahedra, corners with two equivalent O(3)Li2CuP tetrahedra, and corners with two equivalent O(7)LiCu2P tetrahedra. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(2), one Cu(1), one Cu(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Cu(1), one Cu(2), and one P(2) atom. In the seventh O site, O(7) is bonded to one Li(1), one Cu(2), one Cu(3), and one P(2) atom to form distorted OLiCu2P tetrahedra that share corners with two equivalent O(1)Li2CuP tetrahedra, corners with two equivalent O(2)Li2CuP tetrahedra, and corners with two equivalent O(4)Li3P 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(3), and one P(1) atom.
Li3Cu3(PO4)2 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), and one O(7) atom to form LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Cu(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent Cu(2)O4 trigonal pyramids. The Li(1)-O(1) bond length is 2.04 Å. The Li(1)-O(2) bond length is 2.02 Å. The Li(1)-O(4) bond length is 2.12 Å. The Li(1)-O(7) bond length is 2.00 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), and one O(5) 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 Cu(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent Cu(1)O4 trigonal pyramids. The Li(2)-O(1) bond length is 2.01 Å. The Li(2)-O(3) bond length is 2.04 Å. The Li(2)-O(4) bond length is 2.01 Å. The Li(2)-O(5) bond length is 1.96 Å. In the third Li site, Li(3) is bonded to one O(2), one O(3), one O(4), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Cu(1)O4 trigonal pyramids, and corners with two equivalent Cu(2)O4 trigonal pyramids. The Li(3)-O(2) bond length is 2.01 Å. The Li(3)-O(3) bond length is 2.04 Å. The Li(3)-O(4) bond length is 2.00 Å. The Li(3)-O(6) bond length is 2.02 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(3), one O(5), one O(6), and one O(8) atom to form distorted CuO4 trigonal pyramids that share corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Cu(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent Cu(2)O4 trigonal pyramids. The Cu(1)-O(3) bond length is 1.99 Å. The Cu(1)-O(5) bond length is 2.50 Å. The Cu(1)-O(6) bond length is 2.27 Å. The Cu(1)-O(8) bond length is 1.98 Å. In the second Cu site, Cu(2) is bonded to one O(2), one O(6), one O(7), and one O(8) atom to form distorted CuO4 trigonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Cu(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent Cu(1)O4 trigonal pyramids. The Cu(2)-O(2) bond length is 2.23 Å. The Cu(2)-O(6) bond length is 2.03 Å. The Cu(2)-O(7) bond length is 2.00 Å. The Cu(2)-O(8) bond length is 2.25 Å. In the third Cu site, Cu(3) is bonded to one O(1), one O(5), one O(7), and one O(8) atom to form distorted CuO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Cu(1)O4 trigonal pyramids, and corners with two equivalent Cu(2)O4 trigonal pyramids. The Cu(3)-O(1) bond length is 2.26 Å. The Cu(3)-O(5) bond length is 2.04 Å. The Cu(3)-O(7) bond length is 2.07 Å. The Cu(3)-O(8) bond length is 2.16 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), 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 Cu(3)O4 tetrahedra, corners with two equivalent Cu(1)O4 trigonal pyramids, and corners with two equivalent Cu(2)O4 trigonal pyramids. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(8) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(4), one O(5), one O(6), and one O(7) 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 Cu(3)O4 tetrahedra, corners with two equivalent Cu(1)O4 trigonal pyramids, and corners with two equivalent Cu(2)O4 trigonal pyramids. The P(2)-O(4) bond length is 1.56 Å. The P(2)-O(5) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.56 Å. The P(2)-O(7) bond length is 1.58 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Cu(3), and one P(1) atom to form distorted OLi2CuP tetrahedra that share corners with two equivalent O(2)Li2CuP tetrahedra, corners with two equivalent O(3)Li2CuP tetrahedra, corners with two equivalent O(4)Li3P tetrahedra, and corners with two equivalent O(7)LiCu2P tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Cu(2), and one P(1) atom to form distorted OLi2CuP tetrahedra that share corners with two equivalent O(1)Li2CuP tetrahedra, corners with two equivalent O(3)Li2CuP tetrahedra, corners with two equivalent O(4)Li3P tetrahedra, and corners with two equivalent O(7)LiCu2P tetrahedra. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Cu(1), and one P(1) atom to form distorted OLi2CuP tetrahedra that share corners with two equivalent O(1)Li2CuP tetrahedra, corners with two equivalent O(2)Li2CuP tetrahedra, and corners with two equivalent O(4)Li3P tetrahedra. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), and one P(2) atom to form OLi3P tetrahedra that share corners with two equivalent O(1)Li2CuP tetrahedra, corners with two equivalent O(2)Li2CuP tetrahedra, corners with two equivalent O(3)Li2CuP tetrahedra, and corners with two equivalent O(7)LiCu2P tetrahedra. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(2), one Cu(1), one Cu(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Cu(1), one Cu(2), and one P(2) atom. In the seventh O site, O(7) is bonded to one Li(1), one Cu(2), one Cu(3), and one P(2) atom to form distorted OLiCu2P tetrahedra that share corners with two equivalent O(1)Li2CuP tetrahedra, corners with two equivalent O(2)Li2CuP tetrahedra, and corners with two equivalent O(4)Li3P 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(3), and one P(1) atom.