Ta3Zn2Bi3O14 crystallizes in the trigonal R-3m space group. Ta(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form TaO6 octahedra that share corners with two equivalent Zn(1)O6 octahedra and corners with four equivalent Ta(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-57°. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to six equivalent O(1) atoms to form distorted ZnO6 octahedra that share corners with six equivalent Ta(1)O6 octahedra. The corner-sharing octahedral tilt angles are 57°. In the second Zn site, Zn(2) is bonded in a linear geometry to two equivalent O(3) atoms. Bi(1) is bonded in a distorted body-centered cubic geometry to two equivalent O(2), two equivalent O(3), and four equivalent O(1) atoms. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Zn(2) and three equivalent Bi(1) atoms to form distorted OZnBi3 tetrahedra that share corners with four equivalent O(3)ZnBi3 tetrahedra, corners with six equivalent O(1)TaZnBi2 tetrahedra, and edges with three equivalent O(1)TaZnBi2 tetrahedra. In the second O site, O(1) is bonded to one Ta(1), one Zn(1), and two equivalent Bi(1) atoms to form distorted OTaZnBi2 tetrahedra that share corners with two equivalent O(3)ZnBi3 tetrahedra, corners with eight equivalent O(1)TaZnBi2 tetrahedra,  an edgeedge with one O(3)ZnBi3 tetrahedra, and edges with two equivalent O(1)TaZnBi2 tetrahedra. In the third O site, O(2) is bonded in a distorted bent 150 degrees geometry to two equivalent Ta(1) and one Bi(1) atom.
Ta3Zn2Bi3O14 crystallizes in the trigonal R-3m space group. Ta(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form TaO6 octahedra that share corners with two equivalent Zn(1)O6 octahedra and corners with four equivalent Ta(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-57°. Both Ta(1)-O(1) bond lengths are 1.99 Å. All Ta(1)-O(2) bond lengths are 2.00 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to six equivalent O(1) atoms to form distorted ZnO6 octahedra that share corners with six equivalent Ta(1)O6 octahedra. The corner-sharing octahedral tilt angles are 57°. All Zn(1)-O(1) bond lengths are 2.17 Å. In the second Zn site, Zn(2) is bonded in a linear geometry to two equivalent O(3) atoms. Both Zn(2)-O(3) bond lengths are 1.89 Å. Bi(1) is bonded in a distorted body-centered cubic geometry to two equivalent O(2), two equivalent O(3), and four equivalent O(1) atoms. Both Bi(1)-O(2) bond lengths are 2.69 Å. Both Bi(1)-O(3) bond lengths are 2.42 Å. All Bi(1)-O(1) bond lengths are 2.50 Å. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Zn(2) and three equivalent Bi(1) atoms to form distorted OZnBi3 tetrahedra that share corners with four equivalent O(3)ZnBi3 tetrahedra, corners with six equivalent O(1)TaZnBi2 tetrahedra, and edges with three equivalent O(1)TaZnBi2 tetrahedra. In the second O site, O(1) is bonded to one Ta(1), one Zn(1), and two equivalent Bi(1) atoms to form distorted OTaZnBi2 tetrahedra that share corners with two equivalent O(3)ZnBi3 tetrahedra, corners with eight equivalent O(1)TaZnBi2 tetrahedra,  an edgeedge with one O(3)ZnBi3 tetrahedra, and edges with two equivalent O(1)TaZnBi2 tetrahedra. In the third O site, O(2) is bonded in a distorted bent 150 degrees geometry to two equivalent Ta(1) and one Bi(1) atom.