Li4Sn(PO3)6 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(13), one O(15), one O(16), one O(3), and one O(4) atom to form distorted LiO6 octahedra 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(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and  an edgeedge with one Li(3)O5 square pyramid. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one O(11), one O(16), one O(5), and one O(9) atom. In the third Li site, Li(3) is bonded to one O(15), one O(17), one O(3), one O(5), and one O(6) 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(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  an edgeedge with one Li(1)O6 octahedra. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(13), one O(16), one O(17), and one O(5) atom. Sn(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(6), one O(8), and one O(9) atom. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(12), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 46°. In the second P site, P(2) is bonded to one O(11), one O(14), one O(17), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. In the third P site, P(3) is bonded to one O(1), one O(12), one O(2), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 65°. In the fourth P site, P(4) is bonded to one O(1), one O(10), one O(15), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. In the fifth P site, P(5) is bonded to one O(13), one O(14), one O(18), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. In the sixth P site, P(6) is bonded to one O(16), one O(18), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles are 62°. There are eighteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one P(3) and one P(4) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Sn(1) and one P(3) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Sn(1), and one P(3) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Li(1), one Sn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Li(4), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(3), one Sn(1), and one P(5) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(2) and one P(6) atom. In the eighth O site, O(8) is bonded in a single-bond geometry to one Sn(1) and one P(6) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(2), one Sn(1), and one P(4) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one P(1) and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(1), one Li(4), and one P(5) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one P(2) and one P(5) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one P(6) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal non-coplanar geometry to one Li(3), one Li(4), and one P(2) atom. In the eighteenth O site, O(18) is bonded in a bent 120 degrees geometry to one P(5) and one P(6) atom.
Li4Sn(PO3)6 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(13), one O(15), one O(16), one O(3), and one O(4) atom to form distorted LiO6 octahedra 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(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and  an edgeedge with one Li(3)O5 square pyramid. The Li(1)-O(11) bond length is 2.22 Å. The Li(1)-O(13) bond length is 2.50 Å. The Li(1)-O(15) bond length is 2.34 Å. The Li(1)-O(16) bond length is 2.32 Å. The Li(1)-O(3) bond length is 2.51 Å. The Li(1)-O(4) bond length is 2.14 Å. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one O(11), one O(16), one O(5), and one O(9) atom. The Li(2)-O(11) bond length is 1.94 Å. The Li(2)-O(16) bond length is 2.04 Å. The Li(2)-O(5) bond length is 2.01 Å. The Li(2)-O(9) bond length is 2.19 Å. In the third Li site, Li(3) is bonded to one O(15), one O(17), one O(3), one O(5), and one O(6) 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(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  an edgeedge with one Li(1)O6 octahedra. The Li(3)-O(15) bond length is 2.03 Å. The Li(3)-O(17) bond length is 2.18 Å. The Li(3)-O(3) bond length is 2.14 Å. The Li(3)-O(5) bond length is 2.35 Å. The Li(3)-O(6) bond length is 2.03 Å. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(13), one O(16), one O(17), and one O(5) atom. The Li(4)-O(13) bond length is 2.17 Å. The Li(4)-O(16) bond length is 2.00 Å. The Li(4)-O(17) bond length is 2.10 Å. The Li(4)-O(5) bond length is 2.00 Å. Sn(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(6), one O(8), and one O(9) atom. The Sn(1)-O(2) bond length is 2.63 Å. The Sn(1)-O(3) bond length is 2.69 Å. The Sn(1)-O(4) bond length is 2.74 Å. The Sn(1)-O(6) bond length is 2.36 Å. The Sn(1)-O(8) bond length is 2.67 Å. The Sn(1)-O(9) bond length is 2.31 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(12), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 46°. The P(1)-O(10) bond length is 1.65 Å. The P(1)-O(12) bond length is 1.62 Å. The P(1)-O(4) bond length is 1.49 Å. The P(1)-O(5) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(11), one O(14), one O(17), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. The P(2)-O(11) bond length is 1.50 Å. The P(2)-O(14) bond length is 1.64 Å. The P(2)-O(17) bond length is 1.50 Å. The P(2)-O(7) bond length is 1.62 Å. In the third P site, P(3) is bonded to one O(1), one O(12), one O(2), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 65°. The P(3)-O(1) bond length is 1.64 Å. The P(3)-O(12) bond length is 1.63 Å. The P(3)-O(2) bond length is 1.49 Å. The P(3)-O(3) bond length is 1.51 Å. In the fourth P site, P(4) is bonded to one O(1), one O(10), one O(15), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. The P(4)-O(1) bond length is 1.62 Å. The P(4)-O(10) bond length is 1.63 Å. The P(4)-O(15) bond length is 1.48 Å. The P(4)-O(9) bond length is 1.53 Å. In the fifth P site, P(5) is bonded to one O(13), one O(14), one O(18), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. The P(5)-O(13) bond length is 1.49 Å. The P(5)-O(14) bond length is 1.62 Å. The P(5)-O(18) bond length is 1.63 Å. The P(5)-O(6) bond length is 1.53 Å. In the sixth P site, P(6) is bonded to one O(16), one O(18), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles are 62°. The P(6)-O(16) bond length is 1.51 Å. The P(6)-O(18) bond length is 1.63 Å. The P(6)-O(7) bond length is 1.63 Å. The P(6)-O(8) bond length is 1.49 Å. There are eighteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one P(3) and one P(4) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Sn(1) and one P(3) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Sn(1), and one P(3) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Li(1), one Sn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Li(4), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(3), one Sn(1), and one P(5) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(2) and one P(6) atom. In the eighth O site, O(8) is bonded in a single-bond geometry to one Sn(1) and one P(6) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(2), one Sn(1), and one P(4) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one P(1) and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(1), one Li(4), and one P(5) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one P(2) and one P(5) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one P(6) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal non-coplanar geometry to one Li(3), one Li(4), and one P(2) atom. In the eighteenth O site, O(18) is bonded in a bent 120 degrees geometry to one P(5) and one P(6) atom.