Zn(MoO2)2 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(4), two equivalent O(2), and three equivalent O(3) atoms to form a mixture of edge and corner-sharing MoO6 octahedra. The corner-sharing octahedral tilt angles range from 54-62°. In the second Mo site, Mo(2) is bonded to one O(2), two equivalent O(4), and three equivalent O(1) atoms to form a mixture of edge and corner-sharing MoO6 octahedra. The corner-sharing octahedral tilt angles range from 54-62°. Zn(1) is bonded in a 7-coordinate geometry to one O(2), two equivalent O(1), 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 three equivalent Mo(2) and two equivalent Zn(1) atoms to form distorted OZn2Mo3 trigonal bipyramids that share  a cornercorner with one O(2)ZnMo3 tetrahedra, corners with two equivalent O(3)Zn2Mo3 trigonal bipyramids, edges with two equivalent O(2)ZnMo3 tetrahedra,  an edgeedge with one O(3)Zn2Mo3 trigonal bipyramid, and edges with four equivalent O(1)Zn2Mo3 trigonal bipyramids. In the second O site, O(2) is bonded to one Mo(2), two equivalent Mo(1), and one Zn(1) atom to form OZnMo3 tetrahedra that share corners with two equivalent O(2)ZnMo3 tetrahedra,  a cornercorner with one O(1)Zn2Mo3 trigonal bipyramid, corners with six equivalent O(3)Zn2Mo3 trigonal bipyramids,  an edgeedge with one O(3)Zn2Mo3 trigonal bipyramid, and edges with two equivalent O(1)Zn2Mo3 trigonal bipyramids. In the third O site, O(3) is bonded to three equivalent Mo(1) and two equivalent Zn(1) atoms to form distorted OZn2Mo3 trigonal bipyramids that share corners with six equivalent O(2)ZnMo3 tetrahedra, corners with two equivalent O(1)Zn2Mo3 trigonal bipyramids,  an edgeedge with one O(2)ZnMo3 tetrahedra,  an edgeedge with one O(1)Zn2Mo3 trigonal bipyramid, and edges with four equivalent O(3)Zn2Mo3 trigonal bipyramids. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Mo(1), two equivalent Mo(2), and two equivalent Zn(1) atoms.
Zn(MoO2)2 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(4), two equivalent O(2), and three equivalent O(3) atoms to form a mixture of edge and corner-sharing MoO6 octahedra. The corner-sharing octahedral tilt angles range from 54-62°. The Mo(1)-O(4) bond length is 2.19 Å. Both Mo(1)-O(2) bond lengths are 2.10 Å. There is one shorter (2.21 Å) and two longer (2.26 Å) Mo(1)-O(3) bond lengths. In the second Mo site, Mo(2) is bonded to one O(2), two equivalent O(4), and three equivalent O(1) atoms to form a mixture of edge and corner-sharing MoO6 octahedra. The corner-sharing octahedral tilt angles range from 54-62°. The Mo(2)-O(2) bond length is 2.12 Å. Both Mo(2)-O(4) bond lengths are 2.15 Å. There is one shorter (2.18 Å) and two longer (2.21 Å) Mo(2)-O(1) bond lengths. Zn(1) is bonded in a 7-coordinate geometry to one O(2), two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms. The Zn(1)-O(2) bond length is 2.15 Å. Both Zn(1)-O(1) bond lengths are 2.34 Å. Both Zn(1)-O(3) bond lengths are 2.33 Å. Both Zn(1)-O(4) bond lengths are 2.53 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Mo(2) and two equivalent Zn(1) atoms to form distorted OZn2Mo3 trigonal bipyramids that share  a cornercorner with one O(2)ZnMo3 tetrahedra, corners with two equivalent O(3)Zn2Mo3 trigonal bipyramids, edges with two equivalent O(2)ZnMo3 tetrahedra,  an edgeedge with one O(3)Zn2Mo3 trigonal bipyramid, and edges with four equivalent O(1)Zn2Mo3 trigonal bipyramids. In the second O site, O(2) is bonded to one Mo(2), two equivalent Mo(1), and one Zn(1) atom to form OZnMo3 tetrahedra that share corners with two equivalent O(2)ZnMo3 tetrahedra,  a cornercorner with one O(1)Zn2Mo3 trigonal bipyramid, corners with six equivalent O(3)Zn2Mo3 trigonal bipyramids,  an edgeedge with one O(3)Zn2Mo3 trigonal bipyramid, and edges with two equivalent O(1)Zn2Mo3 trigonal bipyramids. In the third O site, O(3) is bonded to three equivalent Mo(1) and two equivalent Zn(1) atoms to form distorted OZn2Mo3 trigonal bipyramids that share corners with six equivalent O(2)ZnMo3 tetrahedra, corners with two equivalent O(1)Zn2Mo3 trigonal bipyramids,  an edgeedge with one O(2)ZnMo3 tetrahedra,  an edgeedge with one O(1)Zn2Mo3 trigonal bipyramid, and edges with four equivalent O(3)Zn2Mo3 trigonal bipyramids. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Mo(1), two equivalent Mo(2), and two equivalent Zn(1) atoms.