BaZn(BiO2)4 crystallizes in the trigonal P-31m space group. Ba(1) is bonded in a distorted hexagonal planar geometry to six equivalent O(1) atoms. Zn(1) is bonded to six equivalent O(1) atoms to form ZnO6 octahedra that share corners with twelve equivalent Bi(1)O4 trigonal pyramids. Bi(1) is bonded to one O(2) and three equivalent O(1) atoms to form BiO4 trigonal pyramids that share corners with three equivalent Zn(1)O6 octahedra and corners with four equivalent Bi(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles are 59°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Ba(1), one Zn(1), and two equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing OBaZnBi2 tetrahedra. In the second O site, O(2) is bonded in a linear geometry to two equivalent Bi(1) atoms.
BaZn(BiO2)4 crystallizes in the trigonal P-31m space group. Ba(1) is bonded in a distorted hexagonal planar geometry to six equivalent O(1) atoms. All Ba(1)-O(1) bond lengths are 2.86 Å. Zn(1) is bonded to six equivalent O(1) atoms to form ZnO6 octahedra that share corners with twelve equivalent Bi(1)O4 trigonal pyramids. All Zn(1)-O(1) bond lengths are 2.27 Å. Bi(1) is bonded to one O(2) and three equivalent O(1) atoms to form BiO4 trigonal pyramids that share corners with three equivalent Zn(1)O6 octahedra and corners with four equivalent Bi(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles are 59°. The Bi(1)-O(2) bond length is 2.10 Å. All Bi(1)-O(1) bond lengths are 2.29 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Ba(1), one Zn(1), and two equivalent Bi(1) atoms to form a mixture of distorted corner and edge-sharing OBaZnBi2 tetrahedra. In the second O site, O(2) is bonded in a linear geometry to two equivalent Bi(1) atoms.