Li4Zn(PS4)2 is Clathrate-derived structured and crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(10), one S(15), one S(3), and one S(6) atom to form LiS4 tetrahedra that share  a cornercorner with one Li(5)S4 tetrahedra,  a cornercorner with one Zn(1)S4 tetrahedra,  a cornercorner with one Zn(2)S4 tetrahedra,  a cornercorner with one P(1)S4 tetrahedra,  a cornercorner with one P(2)S4 tetrahedra, corners with two equivalent P(4)S4 tetrahedra, and corners with two equivalent Li(4)S4 trigonal pyramids. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one S(13), one S(14), one S(3), one S(8), and one S(9) atom. In the third Li site, Li(3) is bonded to one S(11), one S(14), one S(4), and one S(5) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one P(1)S4 tetrahedra,  a cornercorner with one P(3)S4 tetrahedra, corners with two equivalent Li(5)S4 tetrahedra, corners with two equivalent Li(6)S4 tetrahedra, corners with two equivalent P(2)S4 tetrahedra,  a cornercorner with one Li(4)S4 trigonal pyramid, and  an edgeedge with one Li(7)S4 tetrahedra. In the fourth Li site, Li(4) is bonded to one S(11), one S(15), one S(3), and one S(8) atom to form distorted LiS4 trigonal pyramids that share  a cornercorner with one Li(3)S4 tetrahedra,  a cornercorner with one Li(5)S4 tetrahedra,  a cornercorner with one Li(7)S4 tetrahedra,  a cornercorner with one Li(8)S4 tetrahedra, corners with two equivalent Li(1)S4 tetrahedra, corners with two equivalent P(2)S4 tetrahedra, and  an edgeedge with one P(4)S4 tetrahedra. In the fifth Li site, Li(5) is bonded to one S(12), one S(15), one S(4), and one S(5) atom to form LiS4 tetrahedra that share  a cornercorner with one Li(1)S4 tetrahedra,  a cornercorner with one Li(6)S4 tetrahedra,  a cornercorner with one Li(7)S4 tetrahedra,  a cornercorner with one Li(8)S4 tetrahedra,  a cornercorner with one P(2)S4 tetrahedra,  a cornercorner with one P(4)S4 tetrahedra, corners with two equivalent Li(3)S4 tetrahedra, corners with two equivalent P(1)S4 tetrahedra, and  a cornercorner with one Li(4)S4 trigonal pyramid. In the sixth Li site, Li(6) is bonded to one S(14), one S(2), one S(5), and one S(9) atom to form LiS4 tetrahedra that share  a cornercorner with one Li(5)S4 tetrahedra,  a cornercorner with one Zn(1)S4 tetrahedra,  a cornercorner with one Zn(2)S4 tetrahedra,  a cornercorner with one P(2)S4 tetrahedra,  a cornercorner with one P(4)S4 tetrahedra, corners with two equivalent Li(3)S4 tetrahedra, and corners with two equivalent P(3)S4 tetrahedra. In the seventh Li site, Li(7) is bonded to one S(11), one S(16), one S(4), and one S(7) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(5)S4 tetrahedra,  a cornercorner with one Zn(1)S4 tetrahedra,  a cornercorner with one Zn(2)S4 tetrahedra,  a cornercorner with one P(1)S4 tetrahedra,  a cornercorner with one P(3)S4 tetrahedra, corners with two equivalent P(2)S4 tetrahedra,  a cornercorner with one Li(4)S4 trigonal pyramid, and  an edgeedge with one Li(3)S4 tetrahedra. In the eighth Li site, Li(8) is bonded to one S(1), one S(12), one S(13), and one S(8) atom to form LiS4 tetrahedra that share  a cornercorner with one Li(5)S4 tetrahedra,  a cornercorner with one Zn(1)S4 tetrahedra,  a cornercorner with one Zn(2)S4 tetrahedra,  a cornercorner with one P(3)S4 tetrahedra,  a cornercorner with one P(4)S4 tetrahedra, corners with two equivalent P(1)S4 tetrahedra, and  a cornercorner with one Li(4)S4 trigonal pyramid. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(1), one S(16), one S(6), and one S(9) atom to form ZnS4 tetrahedra that share  a cornercorner with one Li(1)S4 tetrahedra,  a cornercorner with one Li(6)S4 tetrahedra,  a cornercorner with one Li(7)S4 tetrahedra,  a cornercorner with one Li(8)S4 tetrahedra,  a cornercorner with one P(1)S4 tetrahedra,  a cornercorner with one P(2)S4 tetrahedra, and corners with two equivalent P(3)S4 tetrahedra. In the second Zn site, Zn(2) is bonded to one S(10), one S(13), one S(2), and one S(7) atom to form ZnS4 tetrahedra that share  a cornercorner with one Li(1)S4 tetrahedra,  a cornercorner with one Li(6)S4 tetrahedra,  a cornercorner with one Li(7)S4 tetrahedra,  a cornercorner with one Li(8)S4 tetrahedra,  a cornercorner with one P(1)S4 tetrahedra,  a cornercorner with one P(3)S4 tetrahedra, and corners with two equivalent P(4)S4 tetrahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one S(12), one S(13), one S(4), and one S(6) atom to form PS4 tetrahedra that share  a cornercorner with one Li(1)S4 tetrahedra,  a cornercorner with one Li(3)S4 tetrahedra,  a cornercorner with one Li(7)S4 tetrahedra,  a cornercorner with one Zn(1)S4 tetrahedra,  a cornercorner with one Zn(2)S4 tetrahedra, corners with two equivalent Li(5)S4 tetrahedra, and corners with two equivalent Li(8)S4 tetrahedra. In the second P site, P(2) is bonded to one S(11), one S(16), one S(3), and one S(5) atom to form PS4 tetrahedra that share  a cornercorner with one Li(1)S4 tetrahedra,  a cornercorner with one Li(5)S4 tetrahedra,  a cornercorner with one Li(6)S4 tetrahedra,  a cornercorner with one Zn(1)S4 tetrahedra, corners with two equivalent Li(3)S4 tetrahedra, corners with two equivalent Li(7)S4 tetrahedra, and corners with two equivalent Li(4)S4 trigonal pyramids. In the third P site, P(3) is bonded to one S(1), one S(14), one S(7), and one S(9) atom to form PS4 tetrahedra that share  a cornercorner with one Li(3)S4 tetrahedra,  a cornercorner with one Li(7)S4 tetrahedra,  a cornercorner with one Li(8)S4 tetrahedra,  a cornercorner with one Zn(2)S4 tetrahedra, corners with two equivalent Li(6)S4 tetrahedra, and corners with two equivalent Zn(1)S4 tetrahedra. In the fourth P site, P(4) is bonded to one S(10), one S(15), one S(2), and one S(8) atom to form PS4 tetrahedra that share  a cornercorner with one Li(5)S4 tetrahedra,  a cornercorner with one Li(6)S4 tetrahedra,  a cornercorner with one Li(8)S4 tetrahedra, corners with two equivalent Li(1)S4 tetrahedra, corners with two equivalent Zn(2)S4 tetrahedra, and  an edgeedge with one Li(4)S4 trigonal pyramid. There are sixteen inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one Li(8), one Zn(1), and one P(3) atom. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to one Li(6), one Zn(2), and one P(4) atom. In the third S site, S(3) is bonded to one Li(1), one Li(2), one Li(4), and one P(2) atom to form SLi3P tetrahedra that share  a cornercorner with one S(9)Li2ZnP tetrahedra,  a cornercorner with one S(5)Li3P tetrahedra, corners with two equivalent S(11)Li3P tetrahedra, corners with two equivalent S(15)Li3P tetrahedra, and  a cornercorner with one S(14)Li3P trigonal pyramid. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one Li(3), one Li(5), one Li(7), and one P(1) atom. In the fifth S site, S(5) is bonded to one Li(3), one Li(5), one Li(6), and one P(2) atom to form SLi3P tetrahedra that share  a cornercorner with one S(9)Li2ZnP tetrahedra,  a cornercorner with one S(15)Li3P tetrahedra,  a cornercorner with one S(3)Li3P tetrahedra, corners with two equivalent S(11)Li3P tetrahedra, and corners with two equivalent S(14)Li3P trigonal pyramids. In the sixth S site, S(6) is bonded in a trigonal non-coplanar geometry to one Li(1), one Zn(1), and one P(1) atom. In the seventh S site, S(7) is bonded in a trigonal non-coplanar geometry to one Li(7), one Zn(2), and one P(3) atom. In the eighth S site, S(8) is bonded in a see-saw-like geometry to one Li(2), one Li(4), one Li(8), and one P(4) atom. In the ninth S site, S(9) is bonded to one Li(2), one Li(6), one Zn(1), and one P(3) atom to form a mixture of distorted corner and edge-sharing SLi2ZnP tetrahedra. In the tenth S site, S(10) is bonded in a trigonal non-coplanar geometry to one Li(1), one Zn(2), and one P(4) atom. In the eleventh S site, S(11) is bonded to one Li(3), one Li(4), one Li(7), and one P(2) atom to form corner-sharing SLi3P tetrahedra. In the twelfth S site, S(12) is bonded in a trigonal non-coplanar geometry to one Li(5), one Li(8), and one P(1) atom. In the thirteenth S site, S(13) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Li(8), one Zn(2), and one P(1) atom. In the fourteenth S site, S(14) is bonded to one Li(2), one Li(3), one Li(6), and one P(3) atom to form distorted SLi3P trigonal pyramids that share  a cornercorner with one S(9)Li2ZnP tetrahedra,  a cornercorner with one S(11)Li3P tetrahedra,  a cornercorner with one S(3)Li3P tetrahedra, corners with two equivalent S(5)Li3P tetrahedra, and  an edgeedge with one S(9)Li2ZnP tetrahedra. In the fifteenth S site, S(15) is bonded to one Li(1), one Li(4), one Li(5), and one P(4) atom to form corner-sharing SLi3P tetrahedra. In the sixteenth S site, S(16) is bonded in a trigonal non-coplanar geometry to one Li(7), one Zn(1), and one P(2) atom.
Li4Zn(PS4)2 is Clathrate-derived structured and crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(10), one S(15), one S(3), and one S(6) atom to form LiS4 tetrahedra that share  a cornercorner with one Li(5)S4 tetrahedra,  a cornercorner with one Zn(1)S4 tetrahedra,  a cornercorner with one Zn(2)S4 tetrahedra,  a cornercorner with one P(1)S4 tetrahedra,  a cornercorner with one P(2)S4 tetrahedra, corners with two equivalent P(4)S4 tetrahedra, and corners with two equivalent Li(4)S4 trigonal pyramids. The Li(1)-S(10) bond length is 2.53 Å. The Li(1)-S(15) bond length is 2.43 Å. The Li(1)-S(3) bond length is 2.48 Å. The Li(1)-S(6) bond length is 2.46 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one S(13), one S(14), one S(3), one S(8), and one S(9) atom. The Li(2)-S(13) bond length is 3.06 Å. The Li(2)-S(14) bond length is 2.85 Å. The Li(2)-S(3) bond length is 2.54 Å. The Li(2)-S(8) bond length is 2.58 Å. The Li(2)-S(9) bond length is 2.76 Å. In the third Li site, Li(3) is bonded to one S(11), one S(14), one S(4), and one S(5) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one P(1)S4 tetrahedra,  a cornercorner with one P(3)S4 tetrahedra, corners with two equivalent Li(5)S4 tetrahedra, corners with two equivalent Li(6)S4 tetrahedra, corners with two equivalent P(2)S4 tetrahedra,  a cornercorner with one Li(4)S4 trigonal pyramid, and  an edgeedge with one Li(7)S4 tetrahedra. The Li(3)-S(11) bond length is 2.53 Å. The Li(3)-S(14) bond length is 2.56 Å. The Li(3)-S(4) bond length is 2.86 Å. The Li(3)-S(5) bond length is 2.49 Å. In the fourth Li site, Li(4) is bonded to one S(11), one S(15), one S(3), and one S(8) atom to form distorted LiS4 trigonal pyramids that share  a cornercorner with one Li(3)S4 tetrahedra,  a cornercorner with one Li(5)S4 tetrahedra,  a cornercorner with one Li(7)S4 tetrahedra,  a cornercorner with one Li(8)S4 tetrahedra, corners with two equivalent Li(1)S4 tetrahedra, corners with two equivalent P(2)S4 tetrahedra, and  an edgeedge with one P(4)S4 tetrahedra. The Li(4)-S(11) bond length is 2.38 Å. The Li(4)-S(15) bond length is 2.56 Å. The Li(4)-S(3) bond length is 2.52 Å. The Li(4)-S(8) bond length is 2.43 Å. In the fifth Li site, Li(5) is bonded to one S(12), one S(15), one S(4), and one S(5) atom to form LiS4 tetrahedra that share  a cornercorner with one Li(1)S4 tetrahedra,  a cornercorner with one Li(6)S4 tetrahedra,  a cornercorner with one Li(7)S4 tetrahedra,  a cornercorner with one Li(8)S4 tetrahedra,  a cornercorner with one P(2)S4 tetrahedra,  a cornercorner with one P(4)S4 tetrahedra, corners with two equivalent Li(3)S4 tetrahedra, corners with two equivalent P(1)S4 tetrahedra, and  a cornercorner with one Li(4)S4 trigonal pyramid. The Li(5)-S(12) bond length is 2.39 Å. The Li(5)-S(15) bond length is 2.46 Å. The Li(5)-S(4) bond length is 2.44 Å. The Li(5)-S(5) bond length is 2.49 Å. In the sixth Li site, Li(6) is bonded to one S(14), one S(2), one S(5), and one S(9) atom to form LiS4 tetrahedra that share  a cornercorner with one Li(5)S4 tetrahedra,  a cornercorner with one Zn(1)S4 tetrahedra,  a cornercorner with one Zn(2)S4 tetrahedra,  a cornercorner with one P(2)S4 tetrahedra,  a cornercorner with one P(4)S4 tetrahedra, corners with two equivalent Li(3)S4 tetrahedra, and corners with two equivalent P(3)S4 tetrahedra. The Li(6)-S(14) bond length is 2.45 Å. The Li(6)-S(2) bond length is 2.42 Å. The Li(6)-S(5) bond length is 2.48 Å. The Li(6)-S(9) bond length is 2.48 Å. In the seventh Li site, Li(7) is bonded to one S(11), one S(16), one S(4), and one S(7) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(5)S4 tetrahedra,  a cornercorner with one Zn(1)S4 tetrahedra,  a cornercorner with one Zn(2)S4 tetrahedra,  a cornercorner with one P(1)S4 tetrahedra,  a cornercorner with one P(3)S4 tetrahedra, corners with two equivalent P(2)S4 tetrahedra,  a cornercorner with one Li(4)S4 trigonal pyramid, and  an edgeedge with one Li(3)S4 tetrahedra. The Li(7)-S(11) bond length is 2.44 Å. The Li(7)-S(16) bond length is 2.47 Å. The Li(7)-S(4) bond length is 2.41 Å. The Li(7)-S(7) bond length is 2.41 Å. In the eighth Li site, Li(8) is bonded to one S(1), one S(12), one S(13), and one S(8) atom to form LiS4 tetrahedra that share  a cornercorner with one Li(5)S4 tetrahedra,  a cornercorner with one Zn(1)S4 tetrahedra,  a cornercorner with one Zn(2)S4 tetrahedra,  a cornercorner with one P(3)S4 tetrahedra,  a cornercorner with one P(4)S4 tetrahedra, corners with two equivalent P(1)S4 tetrahedra, and  a cornercorner with one Li(4)S4 trigonal pyramid. The Li(8)-S(1) bond length is 2.50 Å. The Li(8)-S(12) bond length is 2.38 Å. The Li(8)-S(13) bond length is 2.45 Å. The Li(8)-S(8) bond length is 2.45 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(1), one S(16), one S(6), and one S(9) atom to form ZnS4 tetrahedra that share  a cornercorner with one Li(1)S4 tetrahedra,  a cornercorner with one Li(6)S4 tetrahedra,  a cornercorner with one Li(7)S4 tetrahedra,  a cornercorner with one Li(8)S4 tetrahedra,  a cornercorner with one P(1)S4 tetrahedra,  a cornercorner with one P(2)S4 tetrahedra, and corners with two equivalent P(3)S4 tetrahedra. The Zn(1)-S(1) bond length is 2.37 Å. The Zn(1)-S(16) bond length is 2.36 Å. The Zn(1)-S(6) bond length is 2.35 Å. The Zn(1)-S(9) bond length is 2.41 Å. In the second Zn site, Zn(2) is bonded to one S(10), one S(13), one S(2), and one S(7) atom to form ZnS4 tetrahedra that share  a cornercorner with one Li(1)S4 tetrahedra,  a cornercorner with one Li(6)S4 tetrahedra,  a cornercorner with one Li(7)S4 tetrahedra,  a cornercorner with one Li(8)S4 tetrahedra,  a cornercorner with one P(1)S4 tetrahedra,  a cornercorner with one P(3)S4 tetrahedra, and corners with two equivalent P(4)S4 tetrahedra. The Zn(2)-S(10) bond length is 2.36 Å. The Zn(2)-S(13) bond length is 2.35 Å. The Zn(2)-S(2) bond length is 2.36 Å. The Zn(2)-S(7) bond length is 2.37 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one S(12), one S(13), one S(4), and one S(6) atom to form PS4 tetrahedra that share  a cornercorner with one Li(1)S4 tetrahedra,  a cornercorner with one Li(3)S4 tetrahedra,  a cornercorner with one Li(7)S4 tetrahedra,  a cornercorner with one Zn(1)S4 tetrahedra,  a cornercorner with one Zn(2)S4 tetrahedra, corners with two equivalent Li(5)S4 tetrahedra, and corners with two equivalent Li(8)S4 tetrahedra. The P(1)-S(12) bond length is 2.01 Å. The P(1)-S(13) bond length is 2.11 Å. The P(1)-S(4) bond length is 2.05 Å. The P(1)-S(6) bond length is 2.09 Å. In the second P site, P(2) is bonded to one S(11), one S(16), one S(3), and one S(5) atom to form PS4 tetrahedra that share  a cornercorner with one Li(1)S4 tetrahedra,  a cornercorner with one Li(5)S4 tetrahedra,  a cornercorner with one Li(6)S4 tetrahedra,  a cornercorner with one Zn(1)S4 tetrahedra, corners with two equivalent Li(3)S4 tetrahedra, corners with two equivalent Li(7)S4 tetrahedra, and corners with two equivalent Li(4)S4 trigonal pyramids. The P(2)-S(11) bond length is 2.06 Å. The P(2)-S(16) bond length is 2.07 Å. The P(2)-S(3) bond length is 2.06 Å. The P(2)-S(5) bond length is 2.07 Å. In the third P site, P(3) is bonded to one S(1), one S(14), one S(7), and one S(9) atom to form PS4 tetrahedra that share  a cornercorner with one Li(3)S4 tetrahedra,  a cornercorner with one Li(7)S4 tetrahedra,  a cornercorner with one Li(8)S4 tetrahedra,  a cornercorner with one Zn(2)S4 tetrahedra, corners with two equivalent Li(6)S4 tetrahedra, and corners with two equivalent Zn(1)S4 tetrahedra. The P(3)-S(1) bond length is 2.06 Å. The P(3)-S(14) bond length is 2.04 Å. The P(3)-S(7) bond length is 2.06 Å. The P(3)-S(9) bond length is 2.11 Å. In the fourth P site, P(4) is bonded to one S(10), one S(15), one S(2), and one S(8) atom to form PS4 tetrahedra that share  a cornercorner with one Li(5)S4 tetrahedra,  a cornercorner with one Li(6)S4 tetrahedra,  a cornercorner with one Li(8)S4 tetrahedra, corners with two equivalent Li(1)S4 tetrahedra, corners with two equivalent Zn(2)S4 tetrahedra, and  an edgeedge with one Li(4)S4 trigonal pyramid. The P(4)-S(10) bond length is 2.10 Å. The P(4)-S(15) bond length is 2.05 Å. The P(4)-S(2) bond length is 2.06 Å. The P(4)-S(8) bond length is 2.05 Å. There are sixteen inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one Li(8), one Zn(1), and one P(3) atom. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to one Li(6), one Zn(2), and one P(4) atom. In the third S site, S(3) is bonded to one Li(1), one Li(2), one Li(4), and one P(2) atom to form SLi3P tetrahedra that share  a cornercorner with one S(9)Li2ZnP tetrahedra,  a cornercorner with one S(5)Li3P tetrahedra, corners with two equivalent S(11)Li3P tetrahedra, corners with two equivalent S(15)Li3P tetrahedra, and  a cornercorner with one S(14)Li3P trigonal pyramid. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one Li(3), one Li(5), one Li(7), and one P(1) atom. In the fifth S site, S(5) is bonded to one Li(3), one Li(5), one Li(6), and one P(2) atom to form SLi3P tetrahedra that share  a cornercorner with one S(9)Li2ZnP tetrahedra,  a cornercorner with one S(15)Li3P tetrahedra,  a cornercorner with one S(3)Li3P tetrahedra, corners with two equivalent S(11)Li3P tetrahedra, and corners with two equivalent S(14)Li3P trigonal pyramids. In the sixth S site, S(6) is bonded in a trigonal non-coplanar geometry to one Li(1), one Zn(1), and one P(1) atom. In the seventh S site, S(7) is bonded in a trigonal non-coplanar geometry to one Li(7), one Zn(2), and one P(3) atom. In the eighth S site, S(8) is bonded in a see-saw-like geometry to one Li(2), one Li(4), one Li(8), and one P(4) atom. In the ninth S site, S(9) is bonded to one Li(2), one Li(6), one Zn(1), and one P(3) atom to form a mixture of distorted corner and edge-sharing SLi2ZnP tetrahedra. In the tenth S site, S(10) is bonded in a trigonal non-coplanar geometry to one Li(1), one Zn(2), and one P(4) atom. In the eleventh S site, S(11) is bonded to one Li(3), one Li(4), one Li(7), and one P(2) atom to form corner-sharing SLi3P tetrahedra. In the twelfth S site, S(12) is bonded in a trigonal non-coplanar geometry to one Li(5), one Li(8), and one P(1) atom. In the thirteenth S site, S(13) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Li(8), one Zn(2), and one P(1) atom. In the fourteenth S site, S(14) is bonded to one Li(2), one Li(3), one Li(6), and one P(3) atom to form distorted SLi3P trigonal pyramids that share  a cornercorner with one S(9)Li2ZnP tetrahedra,  a cornercorner with one S(11)Li3P tetrahedra,  a cornercorner with one S(3)Li3P tetrahedra, corners with two equivalent S(5)Li3P tetrahedra, and  an edgeedge with one S(9)Li2ZnP tetrahedra. In the fifteenth S site, S(15) is bonded to one Li(1), one Li(4), one Li(5), and one P(4) atom to form corner-sharing SLi3P tetrahedra. In the sixteenth S site, S(16) is bonded in a trigonal non-coplanar geometry to one Li(7), one Zn(1), and one P(2) atom.