Li5Sn(P2O7)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(4), one O(6), one O(8), and one O(9) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. In the second Li site, Li(2) is bonded in a distorted T-shaped geometry to one O(1), one O(14), and one O(6) atom. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(13), one O(2), one O(3), one O(5), and one O(9) atom. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one O(5), one O(8), and two equivalent O(13) atoms. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one O(11), one O(12), one O(6), and two equivalent O(14) atoms. Sn(1) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(12), one O(2), one O(3), one O(4), and one O(5) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one P(3)O4 tetrahedra and  a cornercorner with one Li(1)O5 trigonal bipyramid. In the second P site, P(2) is bonded to one O(1), one O(10), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one P(4)O4 tetrahedra and corners with two equivalent Li(1)O5 trigonal bipyramids. In the third P site, P(3) is bonded to one O(11), one O(13), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra and  a cornercorner with one Li(1)O5 trigonal bipyramid. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(14), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra and  a cornercorner with one Li(1)O5 trigonal bipyramid. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Sn(1), and one P(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Sn(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted linear geometry to one Li(3), one Sn(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Sn(1), and one P(2) atom. In the fifth O site, O(5) is bonded to one Li(3), one Li(4), one Sn(1), and one P(1) atom to form a mixture of distorted edge and corner-sharing OLi2SnP trigonal pyramids. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(5), and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(4), and one P(4) atom. In the ninth O site, O(9) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(3), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one P(2) and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(5), one Sn(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(5), one Sn(1), and one P(4) atom. In the thirteenth O site, O(13) is bonded to one Li(3), two equivalent Li(4), and one P(3) atom to form distorted OLi3P trigonal pyramids that share  a cornercorner with one O(5)Li2SnP trigonal pyramid,  an edgeedge with one O(5)Li2SnP trigonal pyramid, and  an edgeedge with one O(13)Li3P trigonal pyramid. In the fourteenth O site, O(14) is bonded to one Li(2), two equivalent Li(5), and one P(4) atom to form distorted edge-sharing OLi3P trigonal pyramids.
Li5Sn(P2O7)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(4), one O(6), one O(8), and one O(9) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Li(1)-O(2) bond length is 2.58 Å. The Li(1)-O(4) bond length is 2.16 Å. The Li(1)-O(6) bond length is 2.07 Å. The Li(1)-O(8) bond length is 2.01 Å. The Li(1)-O(9) bond length is 2.04 Å. In the second Li site, Li(2) is bonded in a distorted T-shaped geometry to one O(1), one O(14), and one O(6) atom. The Li(2)-O(1) bond length is 1.97 Å. The Li(2)-O(14) bond length is 2.07 Å. The Li(2)-O(6) bond length is 1.95 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(13), one O(2), one O(3), one O(5), and one O(9) atom. The Li(3)-O(13) bond length is 2.10 Å. The Li(3)-O(2) bond length is 2.38 Å. The Li(3)-O(3) bond length is 1.98 Å. The Li(3)-O(5) bond length is 2.51 Å. The Li(3)-O(9) bond length is 2.03 Å. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one O(5), one O(8), and two equivalent O(13) atoms. The Li(4)-O(5) bond length is 2.03 Å. The Li(4)-O(8) bond length is 2.05 Å. There is one shorter (2.05 Å) and one longer (2.23 Å) Li(4)-O(13) bond length. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one O(11), one O(12), one O(6), and two equivalent O(14) atoms. The Li(5)-O(11) bond length is 1.99 Å. The Li(5)-O(12) bond length is 2.19 Å. The Li(5)-O(6) bond length is 2.10 Å. There is one shorter (2.24 Å) and one longer (2.45 Å) Li(5)-O(14) bond length. Sn(1) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(12), one O(2), one O(3), one O(4), and one O(5) atom. The Sn(1)-O(1) bond length is 2.52 Å. The Sn(1)-O(11) bond length is 2.29 Å. The Sn(1)-O(12) bond length is 2.16 Å. The Sn(1)-O(2) bond length is 2.44 Å. The Sn(1)-O(3) bond length is 2.71 Å. The Sn(1)-O(4) bond length is 2.41 Å. The Sn(1)-O(5) bond length is 2.25 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one P(3)O4 tetrahedra and  a cornercorner with one Li(1)O5 trigonal bipyramid. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.51 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(7) bond length is 1.61 Å. In the second P site, P(2) is bonded to one O(1), one O(10), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one P(4)O4 tetrahedra and corners with two equivalent Li(1)O5 trigonal bipyramids. The P(2)-O(1) bond length is 1.53 Å. The P(2)-O(10) bond length is 1.61 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(11), one O(13), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra and  a cornercorner with one Li(1)O5 trigonal bipyramid. The P(3)-O(11) bond length is 1.55 Å. The P(3)-O(13) bond length is 1.54 Å. The P(3)-O(7) bond length is 1.64 Å. The P(3)-O(9) bond length is 1.52 Å. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(14), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra and  a cornercorner with one Li(1)O5 trigonal bipyramid. The P(4)-O(10) bond length is 1.62 Å. The P(4)-O(12) bond length is 1.56 Å. The P(4)-O(14) bond length is 1.53 Å. The P(4)-O(8) bond length is 1.51 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Sn(1), and one P(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Sn(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted linear geometry to one Li(3), one Sn(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Sn(1), and one P(2) atom. In the fifth O site, O(5) is bonded to one Li(3), one Li(4), one Sn(1), and one P(1) atom to form a mixture of distorted edge and corner-sharing OLi2SnP trigonal pyramids. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(5), and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(4), and one P(4) atom. In the ninth O site, O(9) is bonded in a trigonal non-coplanar geometry to one Li(1), one Li(3), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one P(2) and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(5), one Sn(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(5), one Sn(1), and one P(4) atom. In the thirteenth O site, O(13) is bonded to one Li(3), two equivalent Li(4), and one P(3) atom to form distorted OLi3P trigonal pyramids that share  a cornercorner with one O(5)Li2SnP trigonal pyramid,  an edgeedge with one O(5)Li2SnP trigonal pyramid, and  an edgeedge with one O(13)Li3P trigonal pyramid. In the fourteenth O site, O(14) is bonded to one Li(2), two equivalent Li(5), and one P(4) atom to form distorted edge-sharing OLi3P trigonal pyramids.