TiZn(BiO3)2 crystallizes in the orthorhombic Amm2 space group. Ti(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form TiO4 tetrahedra that share corners with six equivalent Bi(1)O5 square pyramids and corners with two equivalent Zn(1)O4 tetrahedra. Zn(1) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form ZnO4 tetrahedra that share corners with six equivalent Bi(1)O5 square pyramids and corners with two equivalent Ti(1)O4 tetrahedra. Bi(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form distorted BiO5 square pyramids that share corners with three equivalent Ti(1)O4 tetrahedra, corners with three equivalent Zn(1)O4 tetrahedra, and edges with two equivalent Bi(1)O5 square pyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Zn(1) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Ti(1) and two equivalent Bi(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Ti(1), one Zn(1), and one Bi(1) atom.
TiZn(BiO3)2 crystallizes in the orthorhombic Amm2 space group. Ti(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form TiO4 tetrahedra that share corners with six equivalent Bi(1)O5 square pyramids and corners with two equivalent Zn(1)O4 tetrahedra. Both Ti(1)-O(2) bond lengths are 1.80 Å. Both Ti(1)-O(3) bond lengths are 1.90 Å. Zn(1) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form ZnO4 tetrahedra that share corners with six equivalent Bi(1)O5 square pyramids and corners with two equivalent Ti(1)O4 tetrahedra. Both Zn(1)-O(1) bond lengths are 1.96 Å. Both Zn(1)-O(3) bond lengths are 2.05 Å. Bi(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form distorted BiO5 square pyramids that share corners with three equivalent Ti(1)O4 tetrahedra, corners with three equivalent Zn(1)O4 tetrahedra, and edges with two equivalent Bi(1)O5 square pyramids. The Bi(1)-O(3) bond length is 2.17 Å. Both Bi(1)-O(1) bond lengths are 2.23 Å. Both Bi(1)-O(2) bond lengths are 2.51 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Zn(1) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Ti(1) and two equivalent Bi(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Ti(1), one Zn(1), and one Bi(1) atom.