Zn(MoO2)4 crystallizes in the trigonal R-3m space group. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MoO6 octahedra that share edges with two equivalent Mo(2)O6 octahedra, edges with two equivalent Zn(1)O6 octahedra, and edges with four equivalent Mo(1)O6 octahedra. In the second Mo site, Mo(2) is bonded to six equivalent O(1) atoms to form MoO6 octahedra that share corners with six equivalent Zn(1)O6 octahedra and edges with six equivalent Mo(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. Zn(1) is bonded to six equivalent O(1) atoms to form ZnO6 octahedra that share corners with six equivalent Mo(2)O6 octahedra and edges with six equivalent Mo(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Mo(2), two equivalent Mo(1), and one Zn(1) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to three equivalent Mo(1) atoms.
Zn(MoO2)4 crystallizes in the trigonal R-3m space group. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MoO6 octahedra that share edges with two equivalent Mo(2)O6 octahedra, edges with two equivalent Zn(1)O6 octahedra, and edges with four equivalent Mo(1)O6 octahedra. Both Mo(1)-O(2) bond lengths are 2.08 Å. All Mo(1)-O(1) bond lengths are 2.12 Å. In the second Mo site, Mo(2) is bonded to six equivalent O(1) atoms to form MoO6 octahedra that share corners with six equivalent Zn(1)O6 octahedra and edges with six equivalent Mo(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. All Mo(2)-O(1) bond lengths are 2.23 Å. Zn(1) is bonded to six equivalent O(1) atoms to form ZnO6 octahedra that share corners with six equivalent Mo(2)O6 octahedra and edges with six equivalent Mo(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. All Zn(1)-O(1) bond lengths are 2.25 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Mo(2), two equivalent Mo(1), and one Zn(1) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to three equivalent Mo(1) atoms.