Zn(W2O3)2 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form WO5 square pyramids that share corners with four equivalent W(2)O6 octahedra, corners with two equivalent W(1)O5 square pyramids, edges with three equivalent W(2)O6 octahedra, and edges with three equivalent W(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 32-90°. In the second W site, W(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted WO6 octahedra that share corners with two equivalent W(2)O6 octahedra, corners with four equivalent W(1)O5 square pyramids, edges with two equivalent W(2)O6 octahedra, and edges with three equivalent W(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 0-48°. Zn(1) is bonded in a distorted see-saw-like geometry to two equivalent O(3) and two equivalent O(4) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent W(2) and four equivalent W(1) atoms to form OW6 octahedra that share corners with two equivalent O(4)Zn2W2 tetrahedra, corners with eight equivalent O(3)ZnW4 trigonal bipyramids, edges with two equivalent O(1)W6 octahedra, and edges with two equivalent O(3)ZnW4 trigonal bipyramids. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one W(1) and two equivalent W(2) atoms. In the third O site, O(3) is bonded to two equivalent W(1), two equivalent W(2), and one Zn(1) atom to form distorted OZnW4 trigonal bipyramids that share corners with four equivalent O(1)W6 octahedra,  a cornercorner with one O(3)ZnW4 trigonal bipyramid,  an edgeedge with one O(1)W6 octahedra, edges with two equivalent O(4)Zn2W2 tetrahedra, and edges with two equivalent O(3)ZnW4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 16-73°. In the fourth O site, O(4) is bonded to two equivalent W(2) and two equivalent Zn(1) atoms to form OZn2W2 tetrahedra that share corners with two equivalent O(1)W6 octahedra, corners with two equivalent O(4)Zn2W2 tetrahedra, and edges with four equivalent O(3)ZnW4 trigonal bipyramids. The corner-sharing octahedral tilt angles are 5°.
Zn(W2O3)2 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form WO5 square pyramids that share corners with four equivalent W(2)O6 octahedra, corners with two equivalent W(1)O5 square pyramids, edges with three equivalent W(2)O6 octahedra, and edges with three equivalent W(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 32-90°. The W(1)-O(2) bond length is 2.11 Å. Both W(1)-O(1) bond lengths are 2.36 Å. Both W(1)-O(3) bond lengths are 2.28 Å. In the second W site, W(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted WO6 octahedra that share corners with two equivalent W(2)O6 octahedra, corners with four equivalent W(1)O5 square pyramids, edges with two equivalent W(2)O6 octahedra, and edges with three equivalent W(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 0-48°. The W(2)-O(1) bond length is 2.53 Å. The W(2)-O(4) bond length is 2.11 Å. Both W(2)-O(2) bond lengths are 2.11 Å. Both W(2)-O(3) bond lengths are 2.35 Å. Zn(1) is bonded in a distorted see-saw-like geometry to two equivalent O(3) and two equivalent O(4) atoms. Both Zn(1)-O(3) bond lengths are 2.13 Å. Both Zn(1)-O(4) bond lengths are 2.05 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent W(2) and four equivalent W(1) atoms to form OW6 octahedra that share corners with two equivalent O(4)Zn2W2 tetrahedra, corners with eight equivalent O(3)ZnW4 trigonal bipyramids, edges with two equivalent O(1)W6 octahedra, and edges with two equivalent O(3)ZnW4 trigonal bipyramids. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one W(1) and two equivalent W(2) atoms. In the third O site, O(3) is bonded to two equivalent W(1), two equivalent W(2), and one Zn(1) atom to form distorted OZnW4 trigonal bipyramids that share corners with four equivalent O(1)W6 octahedra,  a cornercorner with one O(3)ZnW4 trigonal bipyramid,  an edgeedge with one O(1)W6 octahedra, edges with two equivalent O(4)Zn2W2 tetrahedra, and edges with two equivalent O(3)ZnW4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 16-73°. In the fourth O site, O(4) is bonded to two equivalent W(2) and two equivalent Zn(1) atoms to form OZn2W2 tetrahedra that share corners with two equivalent O(1)W6 octahedra, corners with two equivalent O(4)Zn2W2 tetrahedra, and edges with four equivalent O(3)ZnW4 trigonal bipyramids. The corner-sharing octahedral tilt angles are 5°.