Li4Cu(PO3)6 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(17), one O(7), and one O(8) atom. In the second Li site, Li(2) is bonded to one O(17), one O(18), one O(2), one O(4), and one O(5) atom to form LiO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  an edgeedge with one Li(3)O5 square pyramid, and  an edgeedge with one Li(4)O5 square pyramid. In the third Li site, Li(3) is bonded to one O(14), one O(15), one O(4), one O(5), and one O(7) atom to form distorted LiO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  an edgeedge with one Li(2)O5 square pyramid, and  an edgeedge with one Li(4)O5 square pyramid. In the fourth Li site, Li(4) is bonded to one O(1), one O(14), one O(15), one O(17), and one O(2) atom to form LiO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  an edgeedge with one Li(2)O5 square pyramid, and  an edgeedge with one Li(3)O5 square pyramid. Cu(1) is bonded in a rectangular see-saw-like geometry to one O(11), one O(12), one O(18), and one O(2) atom. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. In the second P site, P(2) is bonded to one O(2), one O(3), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. In the third P site, P(3) is bonded to one O(11), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. In the fourth P site, P(4) is bonded to one O(10), one O(13), one O(14), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the fifth P site, P(5) is bonded to one O(10), one O(12), one O(16), and one O(17) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. In the sixth P site, P(6) is bonded to one O(13), one O(15), one O(16), and one O(18) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. There are eighteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(4), and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(4), one Cu(1), and one P(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(3) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one P(4) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one P(4) and one P(5) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one Cu(1) and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Cu(1) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one P(4) and one P(6) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Li(3), one Li(4), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(4), and one P(6) atom. In the sixteenth O site, O(16) is bonded in a bent 120 degrees geometry to one P(5) and one P(6) atom. In the seventeenth O site, O(17) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal planar geometry to one Li(2), one Cu(1), and one P(6) atom.
Li4Cu(PO3)6 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(17), one O(7), and one O(8) atom. The Li(1)-O(1) bond length is 2.04 Å. The Li(1)-O(17) bond length is 2.02 Å. The Li(1)-O(7) bond length is 2.11 Å. The Li(1)-O(8) bond length is 2.45 Å. In the second Li site, Li(2) is bonded to one O(17), one O(18), one O(2), one O(4), and one O(5) atom to form LiO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  an edgeedge with one Li(3)O5 square pyramid, and  an edgeedge with one Li(4)O5 square pyramid. The Li(2)-O(17) bond length is 2.35 Å. The Li(2)-O(18) bond length is 2.19 Å. The Li(2)-O(2) bond length is 2.30 Å. The Li(2)-O(4) bond length is 2.02 Å. The Li(2)-O(5) bond length is 2.05 Å. In the third Li site, Li(3) is bonded to one O(14), one O(15), one O(4), one O(5), and one O(7) atom to form distorted LiO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  an edgeedge with one Li(2)O5 square pyramid, and  an edgeedge with one Li(4)O5 square pyramid. The Li(3)-O(14) bond length is 2.45 Å. The Li(3)-O(15) bond length is 2.10 Å. The Li(3)-O(4) bond length is 2.08 Å. The Li(3)-O(5) bond length is 2.12 Å. The Li(3)-O(7) bond length is 2.39 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(14), one O(15), one O(17), and one O(2) atom to form LiO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  an edgeedge with one Li(2)O5 square pyramid, and  an edgeedge with one Li(3)O5 square pyramid. The Li(4)-O(1) bond length is 2.03 Å. The Li(4)-O(14) bond length is 1.98 Å. The Li(4)-O(15) bond length is 2.17 Å. The Li(4)-O(17) bond length is 2.30 Å. The Li(4)-O(2) bond length is 2.41 Å. Cu(1) is bonded in a rectangular see-saw-like geometry to one O(11), one O(12), one O(18), and one O(2) atom. The Cu(1)-O(11) bond length is 2.06 Å. The Cu(1)-O(12) bond length is 1.93 Å. The Cu(1)-O(18) bond length is 1.94 Å. The Cu(1)-O(2) bond length is 2.06 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The P(1)-O(1) bond length is 1.50 Å. The P(1)-O(3) bond length is 1.64 Å. The P(1)-O(4) bond length is 1.49 Å. The P(1)-O(6) bond length is 1.62 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(3) bond length is 1.62 Å. The P(2)-O(7) bond length is 1.49 Å. The P(2)-O(9) bond length is 1.63 Å. In the third P site, P(3) is bonded to one O(11), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The P(3)-O(11) bond length is 1.51 Å. The P(3)-O(5) bond length is 1.50 Å. The P(3)-O(6) bond length is 1.61 Å. The P(3)-O(9) bond length is 1.63 Å. In the fourth P site, P(4) is bonded to one O(10), one O(13), one O(14), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The P(4)-O(10) bond length is 1.65 Å. The P(4)-O(13) bond length is 1.65 Å. The P(4)-O(14) bond length is 1.51 Å. The P(4)-O(8) bond length is 1.48 Å. In the fifth P site, P(5) is bonded to one O(10), one O(12), one O(16), and one O(17) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The P(5)-O(10) bond length is 1.61 Å. The P(5)-O(12) bond length is 1.50 Å. The P(5)-O(16) bond length is 1.62 Å. The P(5)-O(17) bond length is 1.50 Å. In the sixth P site, P(6) is bonded to one O(13), one O(15), one O(16), and one O(18) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The P(6)-O(13) bond length is 1.60 Å. The P(6)-O(15) bond length is 1.49 Å. The P(6)-O(16) bond length is 1.62 Å. The P(6)-O(18) bond length is 1.53 Å. There are eighteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(4), and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(4), one Cu(1), and one P(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(3) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one P(4) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one P(4) and one P(5) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one Cu(1) and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Cu(1) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one P(4) and one P(6) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Li(3), one Li(4), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Li(3), one Li(4), and one P(6) atom. In the sixteenth O site, O(16) is bonded in a bent 120 degrees geometry to one P(5) and one P(6) atom. In the seventeenth O site, O(17) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal planar geometry to one Li(2), one Cu(1), and one P(6) atom.