LiZn(SbO2)4 crystallizes in the triclinic P1 space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(5), and two equivalent O(6) atoms. Zn(1) is bonded to one O(3), one O(7), one O(8), and two equivalent O(6) atoms to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one Sb(1)O5 square pyramid, corners with two equivalent Sb(4)O5 square pyramids, corners with two equivalent Zn(1)O5 trigonal bipyramids, and edges with two equivalent Sb(3)O6 octahedra. There are four inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one O(7), two equivalent O(4), and two equivalent O(5) atoms to form distorted SbO5 square pyramids that share  a cornercorner with one Zn(1)O5 trigonal bipyramid, edges with two equivalent Sb(1)O5 square pyramids, and edges with two equivalent Sb(4)O5 square pyramids. In the second Sb site, Sb(2) is bonded in a 3-coordinate geometry to one O(4) and two equivalent O(3) atoms. In the third Sb site, Sb(3) is bonded to one O(1), one O(6), two equivalent O(2), and two equivalent O(8) atoms to form SbO6 octahedra that share corners with two equivalent Sb(4)O5 square pyramids, edges with two equivalent Sb(3)O6 octahedra, and edges with two equivalent Zn(1)O5 trigonal bipyramids. In the fourth Sb site, Sb(4) is bonded to one O(5), two equivalent O(1), and two equivalent O(7) atoms to form distorted SbO5 square pyramids that share corners with two equivalent Sb(3)O6 octahedra, corners with two equivalent Zn(1)O5 trigonal bipyramids, edges with two equivalent Sb(1)O5 square pyramids, and edges with two equivalent Sb(4)O5 square pyramids. The corner-sharing octahedral tilt angles are 63°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Sb(3) and two equivalent Sb(4) atoms. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1) and two equivalent Sb(3) atoms. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Zn(1) and two equivalent Sb(2) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Sb(2) and two equivalent Sb(1) atoms. In the fifth O site, O(5) is bonded to one Li(1), one Sb(4), and two equivalent Sb(1) atoms to form distorted OLiSb3 tetrahedra that share corners with two equivalent O(6)Li2Zn2Sb square pyramids, corners with two equivalent O(5)LiSb3 tetrahedra, and edges with two equivalent O(7)ZnSb3 tetrahedra. In the sixth O site, O(6) is bonded to two equivalent Li(1), two equivalent Zn(1), and one Sb(3) atom to form OLi2Zn2Sb square pyramids that share corners with two equivalent O(5)LiSb3 tetrahedra, corners with two equivalent O(7)ZnSb3 tetrahedra, and edges with two equivalent O(6)Li2Zn2Sb square pyramids. In the seventh O site, O(7) is bonded to one Zn(1), one Sb(1), and two equivalent Sb(4) atoms to form distorted OZnSb3 tetrahedra that share corners with two equivalent O(6)Li2Zn2Sb square pyramids, corners with two equivalent O(7)ZnSb3 tetrahedra, and edges with two equivalent O(5)LiSb3 tetrahedra. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Zn(1) and two equivalent Sb(3) atoms.
LiZn(SbO2)4 crystallizes in the triclinic P1 space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(5), and two equivalent O(6) atoms. The Li(1)-O(2) bond length is 1.96 Å. The Li(1)-O(5) bond length is 1.97 Å. There is one shorter (2.28 Å) and one longer (2.37 Å) Li(1)-O(6) bond length. Zn(1) is bonded to one O(3), one O(7), one O(8), and two equivalent O(6) atoms to form distorted ZnO5 trigonal bipyramids that share  a cornercorner with one Sb(1)O5 square pyramid, corners with two equivalent Sb(4)O5 square pyramids, corners with two equivalent Zn(1)O5 trigonal bipyramids, and edges with two equivalent Sb(3)O6 octahedra. The Zn(1)-O(3) bond length is 2.20 Å. The Zn(1)-O(7) bond length is 1.99 Å. The Zn(1)-O(8) bond length is 2.36 Å. Both Zn(1)-O(6) bond lengths are 2.10 Å. There are four inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one O(7), two equivalent O(4), and two equivalent O(5) atoms to form distorted SbO5 square pyramids that share  a cornercorner with one Zn(1)O5 trigonal bipyramid, edges with two equivalent Sb(1)O5 square pyramids, and edges with two equivalent Sb(4)O5 square pyramids. The Sb(1)-O(7) bond length is 2.06 Å. There is one shorter (2.18 Å) and one longer (2.26 Å) Sb(1)-O(4) bond length. There is one shorter (2.27 Å) and one longer (2.37 Å) Sb(1)-O(5) bond length. In the second Sb site, Sb(2) is bonded in a 3-coordinate geometry to one O(4) and two equivalent O(3) atoms. The Sb(2)-O(4) bond length is 2.01 Å. Both Sb(2)-O(3) bond lengths are 2.10 Å. In the third Sb site, Sb(3) is bonded to one O(1), one O(6), two equivalent O(2), and two equivalent O(8) atoms to form SbO6 octahedra that share corners with two equivalent Sb(4)O5 square pyramids, edges with two equivalent Sb(3)O6 octahedra, and edges with two equivalent Zn(1)O5 trigonal bipyramids. The Sb(3)-O(1) bond length is 2.18 Å. The Sb(3)-O(6) bond length is 2.16 Å. There is one shorter (2.12 Å) and one longer (2.13 Å) Sb(3)-O(2) bond length. There is one shorter (2.17 Å) and one longer (2.19 Å) Sb(3)-O(8) bond length. In the fourth Sb site, Sb(4) is bonded to one O(5), two equivalent O(1), and two equivalent O(7) atoms to form distorted SbO5 square pyramids that share corners with two equivalent Sb(3)O6 octahedra, corners with two equivalent Zn(1)O5 trigonal bipyramids, edges with two equivalent Sb(1)O5 square pyramids, and edges with two equivalent Sb(4)O5 square pyramids. The corner-sharing octahedral tilt angles are 63°. The Sb(4)-O(5) bond length is 2.03 Å. There is one shorter (2.17 Å) and one longer (2.19 Å) Sb(4)-O(1) bond length. There is one shorter (2.41 Å) and one longer (2.45 Å) Sb(4)-O(7) bond length. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Sb(3) and two equivalent Sb(4) atoms. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1) and two equivalent Sb(3) atoms. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Zn(1) and two equivalent Sb(2) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Sb(2) and two equivalent Sb(1) atoms. In the fifth O site, O(5) is bonded to one Li(1), one Sb(4), and two equivalent Sb(1) atoms to form distorted OLiSb3 tetrahedra that share corners with two equivalent O(6)Li2Zn2Sb square pyramids, corners with two equivalent O(5)LiSb3 tetrahedra, and edges with two equivalent O(7)ZnSb3 tetrahedra. In the sixth O site, O(6) is bonded to two equivalent Li(1), two equivalent Zn(1), and one Sb(3) atom to form OLi2Zn2Sb square pyramids that share corners with two equivalent O(5)LiSb3 tetrahedra, corners with two equivalent O(7)ZnSb3 tetrahedra, and edges with two equivalent O(6)Li2Zn2Sb square pyramids. In the seventh O site, O(7) is bonded to one Zn(1), one Sb(1), and two equivalent Sb(4) atoms to form distorted OZnSb3 tetrahedra that share corners with two equivalent O(6)Li2Zn2Sb square pyramids, corners with two equivalent O(7)ZnSb3 tetrahedra, and edges with two equivalent O(5)LiSb3 tetrahedra. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Zn(1) and two equivalent Sb(3) atoms.