LiZn4(SnO2)4 crystallizes in the triclinic P1 space group. Li(1) is bonded in a linear geometry to one O(2) and one O(3) atom. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), one O(4), one O(6), and two equivalent O(7) atoms to form a mixture of distorted corner and edge-sharing ZnO5 trigonal bipyramids. In the second Zn site, Zn(2) is bonded to one O(1), one O(4), one O(8), and two equivalent O(5) atoms to form a mixture of distorted corner and edge-sharing ZnO5 trigonal bipyramids. In the third Zn site, Zn(3) is bonded in a distorted see-saw-like geometry to one O(7), one O(8), and two equivalent O(3) atoms. In the fourth Zn site, Zn(4) is bonded in a distorted see-saw-like geometry to one O(5), one O(6), and two equivalent O(2) atoms. There are four inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a distorted trigonal non-coplanar geometry to one O(5) and two equivalent O(4) atoms. In the second Sn site, Sn(2) is bonded in a 3-coordinate geometry to one O(2) and two equivalent O(6) atoms. In the third Sn site, Sn(3) is bonded in a 3-coordinate geometry to one O(3) and two equivalent O(8) atoms. In the fourth Sn site, Sn(4) is bonded in a distorted trigonal non-coplanar geometry to one O(7) and two equivalent O(1) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Zn(1), one Zn(2), and two equivalent Sn(4) atoms to form OZn2Sn2 trigonal pyramids that share  a cornercorner with one O(6)Zn2Sn2 tetrahedra,  a cornercorner with one O(8)Zn2Sn2 tetrahedra, corners with two equivalent O(5)Zn3Sn tetrahedra, corners with two equivalent O(1)Zn2Sn2 trigonal pyramids, edges with two equivalent O(7)Zn3Sn tetrahedra, and  an edgeedge with one O(4)Zn2Sn2 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), two equivalent Zn(4), and one Sn(2) atom to form distorted OLiZn2Sn tetrahedra that share  a cornercorner with one O(3)LiZn2Sn tetrahedra, corners with two equivalent O(2)LiZn2Sn tetrahedra, corners with two equivalent O(5)Zn3Sn tetrahedra, and edges with two equivalent O(6)Zn2Sn2 tetrahedra. In the third O site, O(3) is bonded to one Li(1), two equivalent Zn(3), and one Sn(3) atom to form distorted OLiZn2Sn tetrahedra that share  a cornercorner with one O(2)LiZn2Sn tetrahedra, corners with two equivalent O(3)LiZn2Sn tetrahedra, corners with two equivalent O(7)Zn3Sn tetrahedra, and edges with two equivalent O(8)Zn2Sn2 tetrahedra. In the fourth O site, O(4) is bonded to one Zn(1), one Zn(2), and two equivalent Sn(1) atoms to form OZn2Sn2 trigonal pyramids that share  a cornercorner with one O(6)Zn2Sn2 tetrahedra,  a cornercorner with one O(8)Zn2Sn2 tetrahedra, corners with two equivalent O(7)Zn3Sn tetrahedra, corners with two equivalent O(4)Zn2Sn2 trigonal pyramids, edges with two equivalent O(5)Zn3Sn tetrahedra, and  an edgeedge with one O(1)Zn2Sn2 trigonal pyramid. In the fifth O site, O(5) is bonded to one Zn(4), two equivalent Zn(2), and one Sn(1) atom to form OZn3Sn tetrahedra that share  a cornercorner with one O(6)Zn2Sn2 tetrahedra, corners with two equivalent O(2)LiZn2Sn tetrahedra, corners with two equivalent O(8)Zn2Sn2 tetrahedra, corners with two equivalent O(5)Zn3Sn tetrahedra, corners with two equivalent O(1)Zn2Sn2 trigonal pyramids, and edges with two equivalent O(4)Zn2Sn2 trigonal pyramids. In the sixth O site, O(6) is bonded to one Zn(1), one Zn(4), and two equivalent Sn(2) atoms to form distorted OZn2Sn2 tetrahedra that share  a cornercorner with one O(5)Zn3Sn tetrahedra, corners with two equivalent O(6)Zn2Sn2 tetrahedra, corners with two equivalent O(7)Zn3Sn tetrahedra,  a cornercorner with one O(1)Zn2Sn2 trigonal pyramid,  a cornercorner with one O(4)Zn2Sn2 trigonal pyramid, and edges with two equivalent O(2)LiZn2Sn tetrahedra. In the seventh O site, O(7) is bonded to one Zn(3), two equivalent Zn(1), and one Sn(4) atom to form OZn3Sn tetrahedra that share  a cornercorner with one O(8)Zn2Sn2 tetrahedra, corners with two equivalent O(3)LiZn2Sn tetrahedra, corners with two equivalent O(6)Zn2Sn2 tetrahedra, corners with two equivalent O(7)Zn3Sn tetrahedra, corners with two equivalent O(4)Zn2Sn2 trigonal pyramids, and edges with two equivalent O(1)Zn2Sn2 trigonal pyramids. In the eighth O site, O(8) is bonded to one Zn(2), one Zn(3), and two equivalent Sn(3) atoms to form distorted OZn2Sn2 tetrahedra that share  a cornercorner with one O(7)Zn3Sn tetrahedra, corners with two equivalent O(8)Zn2Sn2 tetrahedra, corners with two equivalent O(5)Zn3Sn tetrahedra,  a cornercorner with one O(1)Zn2Sn2 trigonal pyramid,  a cornercorner with one O(4)Zn2Sn2 trigonal pyramid, and edges with two equivalent O(3)LiZn2Sn tetrahedra.
LiZn4(SnO2)4 crystallizes in the triclinic P1 space group. Li(1) is bonded in a linear geometry to one O(2) and one O(3) atom. The Li(1)-O(2) bond length is 1.84 Å. The Li(1)-O(3) bond length is 1.84 Å. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), one O(4), one O(6), and two equivalent O(7) atoms to form a mixture of distorted corner and edge-sharing ZnO5 trigonal bipyramids. The Zn(1)-O(1) bond length is 2.39 Å. The Zn(1)-O(4) bond length is 2.01 Å. The Zn(1)-O(6) bond length is 2.09 Å. Both Zn(1)-O(7) bond lengths are 2.04 Å. In the second Zn site, Zn(2) is bonded to one O(1), one O(4), one O(8), and two equivalent O(5) atoms to form a mixture of distorted corner and edge-sharing ZnO5 trigonal bipyramids. The Zn(2)-O(1) bond length is 2.01 Å. The Zn(2)-O(4) bond length is 2.40 Å. The Zn(2)-O(8) bond length is 2.09 Å. Both Zn(2)-O(5) bond lengths are 2.04 Å. In the third Zn site, Zn(3) is bonded in a distorted see-saw-like geometry to one O(7), one O(8), and two equivalent O(3) atoms. The Zn(3)-O(7) bond length is 1.96 Å. The Zn(3)-O(8) bond length is 2.10 Å. Both Zn(3)-O(3) bond lengths are 2.02 Å. In the fourth Zn site, Zn(4) is bonded in a distorted see-saw-like geometry to one O(5), one O(6), and two equivalent O(2) atoms. The Zn(4)-O(5) bond length is 1.96 Å. The Zn(4)-O(6) bond length is 2.10 Å. Both Zn(4)-O(2) bond lengths are 2.02 Å. There are four inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a distorted trigonal non-coplanar geometry to one O(5) and two equivalent O(4) atoms. The Sn(1)-O(5) bond length is 2.24 Å. Both Sn(1)-O(4) bond lengths are 2.15 Å. In the second Sn site, Sn(2) is bonded in a 3-coordinate geometry to one O(2) and two equivalent O(6) atoms. The Sn(2)-O(2) bond length is 2.15 Å. Both Sn(2)-O(6) bond lengths are 2.22 Å. In the third Sn site, Sn(3) is bonded in a 3-coordinate geometry to one O(3) and two equivalent O(8) atoms. The Sn(3)-O(3) bond length is 2.15 Å. There is one shorter (2.22 Å) and one longer (2.23 Å) Sn(3)-O(8) bond length. In the fourth Sn site, Sn(4) is bonded in a distorted trigonal non-coplanar geometry to one O(7) and two equivalent O(1) atoms. The Sn(4)-O(7) bond length is 2.24 Å. Both Sn(4)-O(1) bond lengths are 2.15 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Zn(1), one Zn(2), and two equivalent Sn(4) atoms to form OZn2Sn2 trigonal pyramids that share  a cornercorner with one O(6)Zn2Sn2 tetrahedra,  a cornercorner with one O(8)Zn2Sn2 tetrahedra, corners with two equivalent O(5)Zn3Sn tetrahedra, corners with two equivalent O(1)Zn2Sn2 trigonal pyramids, edges with two equivalent O(7)Zn3Sn tetrahedra, and  an edgeedge with one O(4)Zn2Sn2 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), two equivalent Zn(4), and one Sn(2) atom to form distorted OLiZn2Sn tetrahedra that share  a cornercorner with one O(3)LiZn2Sn tetrahedra, corners with two equivalent O(2)LiZn2Sn tetrahedra, corners with two equivalent O(5)Zn3Sn tetrahedra, and edges with two equivalent O(6)Zn2Sn2 tetrahedra. In the third O site, O(3) is bonded to one Li(1), two equivalent Zn(3), and one Sn(3) atom to form distorted OLiZn2Sn tetrahedra that share  a cornercorner with one O(2)LiZn2Sn tetrahedra, corners with two equivalent O(3)LiZn2Sn tetrahedra, corners with two equivalent O(7)Zn3Sn tetrahedra, and edges with two equivalent O(8)Zn2Sn2 tetrahedra. In the fourth O site, O(4) is bonded to one Zn(1), one Zn(2), and two equivalent Sn(1) atoms to form OZn2Sn2 trigonal pyramids that share  a cornercorner with one O(6)Zn2Sn2 tetrahedra,  a cornercorner with one O(8)Zn2Sn2 tetrahedra, corners with two equivalent O(7)Zn3Sn tetrahedra, corners with two equivalent O(4)Zn2Sn2 trigonal pyramids, edges with two equivalent O(5)Zn3Sn tetrahedra, and  an edgeedge with one O(1)Zn2Sn2 trigonal pyramid. In the fifth O site, O(5) is bonded to one Zn(4), two equivalent Zn(2), and one Sn(1) atom to form OZn3Sn tetrahedra that share  a cornercorner with one O(6)Zn2Sn2 tetrahedra, corners with two equivalent O(2)LiZn2Sn tetrahedra, corners with two equivalent O(8)Zn2Sn2 tetrahedra, corners with two equivalent O(5)Zn3Sn tetrahedra, corners with two equivalent O(1)Zn2Sn2 trigonal pyramids, and edges with two equivalent O(4)Zn2Sn2 trigonal pyramids. In the sixth O site, O(6) is bonded to one Zn(1), one Zn(4), and two equivalent Sn(2) atoms to form distorted OZn2Sn2 tetrahedra that share  a cornercorner with one O(5)Zn3Sn tetrahedra, corners with two equivalent O(6)Zn2Sn2 tetrahedra, corners with two equivalent O(7)Zn3Sn tetrahedra,  a cornercorner with one O(1)Zn2Sn2 trigonal pyramid,  a cornercorner with one O(4)Zn2Sn2 trigonal pyramid, and edges with two equivalent O(2)LiZn2Sn tetrahedra. In the seventh O site, O(7) is bonded to one Zn(3), two equivalent Zn(1), and one Sn(4) atom to form OZn3Sn tetrahedra that share  a cornercorner with one O(8)Zn2Sn2 tetrahedra, corners with two equivalent O(3)LiZn2Sn tetrahedra, corners with two equivalent O(6)Zn2Sn2 tetrahedra, corners with two equivalent O(7)Zn3Sn tetrahedra, corners with two equivalent O(4)Zn2Sn2 trigonal pyramids, and edges with two equivalent O(1)Zn2Sn2 trigonal pyramids. In the eighth O site, O(8) is bonded to one Zn(2), one Zn(3), and two equivalent Sn(3) atoms to form distorted OZn2Sn2 tetrahedra that share  a cornercorner with one O(7)Zn3Sn tetrahedra, corners with two equivalent O(8)Zn2Sn2 tetrahedra, corners with two equivalent O(5)Zn3Sn tetrahedra,  a cornercorner with one O(1)Zn2Sn2 trigonal pyramid,  a cornercorner with one O(4)Zn2Sn2 trigonal pyramid, and edges with two equivalent O(3)LiZn2Sn tetrahedra.