Zn(MoO2)2 crystallizes in the orthorhombic Cmcm space group. Mo(1) is bonded to one O(2), two equivalent O(3), and three equivalent O(1) atoms to form a mixture of corner and edge-sharing MoO6 octahedra. The corner-sharing octahedral tilt angles range from 0-63°. Zn(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Mo(1) and two equivalent Zn(1) atoms to form distorted OZn2Mo3 trigonal bipyramids that share corners with five equivalent O(2)Zn2Mo2 tetrahedra, corners with two equivalent O(1)Zn2Mo3 trigonal bipyramids,  an edgeedge with one O(2)Zn2Mo2 tetrahedra, and edges with five equivalent O(1)Zn2Mo3 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Mo(1) and two equivalent Zn(1) atoms to form OZn2Mo2 tetrahedra that share corners with two equivalent O(2)Zn2Mo2 tetrahedra, corners with ten equivalent O(1)Zn2Mo3 trigonal bipyramids, and edges with two equivalent O(1)Zn2Mo3 trigonal bipyramids. In the third O site, O(3) is bonded in a square co-planar geometry to four equivalent Mo(1) atoms.
Zn(MoO2)2 crystallizes in the orthorhombic Cmcm space group. Mo(1) is bonded to one O(2), two equivalent O(3), and three equivalent O(1) atoms to form a mixture of corner and edge-sharing MoO6 octahedra. The corner-sharing octahedral tilt angles range from 0-63°. The Mo(1)-O(2) bond length is 2.17 Å. Both Mo(1)-O(3) bond lengths are 2.21 Å. There are two shorter (2.16 Å) and one longer (2.18 Å) Mo(1)-O(1) bond length. Zn(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Both Zn(1)-O(2) bond lengths are 2.05 Å. All Zn(1)-O(1) bond lengths are 2.48 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Mo(1) and two equivalent Zn(1) atoms to form distorted OZn2Mo3 trigonal bipyramids that share corners with five equivalent O(2)Zn2Mo2 tetrahedra, corners with two equivalent O(1)Zn2Mo3 trigonal bipyramids,  an edgeedge with one O(2)Zn2Mo2 tetrahedra, and edges with five equivalent O(1)Zn2Mo3 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Mo(1) and two equivalent Zn(1) atoms to form OZn2Mo2 tetrahedra that share corners with two equivalent O(2)Zn2Mo2 tetrahedra, corners with ten equivalent O(1)Zn2Mo3 trigonal bipyramids, and edges with two equivalent O(1)Zn2Mo3 trigonal bipyramids. In the third O site, O(3) is bonded in a square co-planar geometry to four equivalent Mo(1) atoms.