Ba2Zn3Tl2(WO3)4 crystallizes in the tetragonal I4/mmm space group. Ba(1) is bonded in a 9-coordinate geometry to one O(3), four equivalent O(1), and four equivalent O(4) atoms. There are two inequivalent W sites. In the first W site, W(1) is bonded in a 4-coordinate geometry to four equivalent Zn(1) and four equivalent O(2) atoms. In the second W site, W(2) is bonded in a distorted square co-planar geometry to four equivalent Zn(1) and four equivalent O(1) atoms. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a 8-coordinate geometry to four equivalent W(1) and four equivalent W(2) atoms. In the second Zn site, Zn(2) is bonded in a body-centered cubic geometry to eight equivalent O(2) atoms. Tl(1) is bonded to one O(4) and five equivalent O(3) atoms to form a mixture of corner and edge-sharing TlO6 octahedra. The corner-sharing octahedral tilt angles are 4°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to two equivalent Ba(1) and two equivalent W(2) atoms. In the second O site, O(2) is bonded to two equivalent W(1) and two equivalent Zn(2) atoms to form a mixture of corner and edge-sharing OZn2W2 tetrahedra. In the third O site, O(3) is bonded to one Ba(1) and five equivalent Tl(1) atoms to form OBaTl5 octahedra that share corners with four equivalent O(3)BaTl5 octahedra,  a cornercorner with one O(4)Ba4Tl square pyramid, edges with eight equivalent O(3)BaTl5 octahedra, and edges with four equivalent O(4)Ba4Tl square pyramids. The corner-sharing octahedral tilt angles are 4°. In the fourth O site, O(4) is bonded to four equivalent Ba(1) and one Tl(1) atom to form distorted OBa4Tl square pyramids that share  a cornercorner with one O(3)BaTl5 octahedra, corners with four equivalent O(4)Ba4Tl square pyramids, edges with four equivalent O(3)BaTl5 octahedra, and edges with four equivalent O(4)Ba4Tl square pyramids. The corner-sharing octahedra are not tilted.
Ba2Zn3Tl2(WO3)4 crystallizes in the tetragonal I4/mmm space group. Ba(1) is bonded in a 9-coordinate geometry to one O(3), four equivalent O(1), and four equivalent O(4) atoms. The Ba(1)-O(3) bond length is 2.91 Å. All Ba(1)-O(1) bond lengths are 2.93 Å. All Ba(1)-O(4) bond lengths are 2.76 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded in a 4-coordinate geometry to four equivalent Zn(1) and four equivalent O(2) atoms. All W(1)-Zn(1) bond lengths are 2.95 Å. All W(1)-O(2) bond lengths are 2.10 Å. In the second W site, W(2) is bonded in a distorted square co-planar geometry to four equivalent Zn(1) and four equivalent O(1) atoms. All W(2)-Zn(1) bond lengths are 3.14 Å. All W(2)-O(1) bond lengths are 1.99 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a 8-coordinate geometry to four equivalent W(1) and four equivalent W(2) atoms. In the second Zn site, Zn(2) is bonded in a body-centered cubic geometry to eight equivalent O(2) atoms. All Zn(2)-O(2) bond lengths are 2.33 Å. Tl(1) is bonded to one O(4) and five equivalent O(3) atoms to form a mixture of corner and edge-sharing TlO6 octahedra. The corner-sharing octahedral tilt angles are 4°. The Tl(1)-O(4) bond length is 2.20 Å. There is one shorter (2.24 Å) and four longer (2.70 Å) Tl(1)-O(3) bond lengths. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to two equivalent Ba(1) and two equivalent W(2) atoms. In the second O site, O(2) is bonded to two equivalent W(1) and two equivalent Zn(2) atoms to form a mixture of corner and edge-sharing OZn2W2 tetrahedra. In the third O site, O(3) is bonded to one Ba(1) and five equivalent Tl(1) atoms to form OBaTl5 octahedra that share corners with four equivalent O(3)BaTl5 octahedra,  a cornercorner with one O(4)Ba4Tl square pyramid, edges with eight equivalent O(3)BaTl5 octahedra, and edges with four equivalent O(4)Ba4Tl square pyramids. The corner-sharing octahedral tilt angles are 4°. In the fourth O site, O(4) is bonded to four equivalent Ba(1) and one Tl(1) atom to form distorted OBa4Tl square pyramids that share  a cornercorner with one O(3)BaTl5 octahedra, corners with four equivalent O(4)Ba4Tl square pyramids, edges with four equivalent O(3)BaTl5 octahedra, and edges with four equivalent O(4)Ba4Tl square pyramids. The corner-sharing octahedra are not tilted.