Zn(AgO2)2 crystallizes in the orthorhombic Cmcm space group. Ag(1) is bonded to one O(2), two equivalent O(3), and three equivalent O(1) atoms to form a mixture of edge and corner-sharing AgO6 octahedra. The corner-sharing octahedral tilt angles range from 0-65°. 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 Ag(1) and two equivalent Zn(1) atoms to form distorted OZn2Ag3 trigonal bipyramids that share corners with five equivalent O(2)Zn2Ag2 tetrahedra, corners with two equivalent O(1)Zn2Ag3 trigonal bipyramids,  an edgeedge with one O(2)Zn2Ag2 tetrahedra, and edges with five equivalent O(1)Zn2Ag3 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Ag(1) and two equivalent Zn(1) atoms to form OZn2Ag2 tetrahedra that share corners with two equivalent O(2)Zn2Ag2 tetrahedra, corners with ten equivalent O(1)Zn2Ag3 trigonal bipyramids, and edges with two equivalent O(1)Zn2Ag3 trigonal bipyramids. In the third O site, O(3) is bonded in a square co-planar geometry to four equivalent Ag(1) atoms.
Zn(AgO2)2 crystallizes in the orthorhombic Cmcm space group. Ag(1) is bonded to one O(2), two equivalent O(3), and three equivalent O(1) atoms to form a mixture of edge and corner-sharing AgO6 octahedra. The corner-sharing octahedral tilt angles range from 0-65°. The Ag(1)-O(2) bond length is 2.10 Å. Both Ag(1)-O(3) bond lengths are 2.20 Å. There is one shorter (2.11 Å) and two longer (2.32 Å) Ag(1)-O(1) bond lengths. 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 2.10 Å. All Zn(1)-O(1) bond lengths are 2.30 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Ag(1) and two equivalent Zn(1) atoms to form distorted OZn2Ag3 trigonal bipyramids that share corners with five equivalent O(2)Zn2Ag2 tetrahedra, corners with two equivalent O(1)Zn2Ag3 trigonal bipyramids,  an edgeedge with one O(2)Zn2Ag2 tetrahedra, and edges with five equivalent O(1)Zn2Ag3 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Ag(1) and two equivalent Zn(1) atoms to form OZn2Ag2 tetrahedra that share corners with two equivalent O(2)Zn2Ag2 tetrahedra, corners with ten equivalent O(1)Zn2Ag3 trigonal bipyramids, and edges with two equivalent O(1)Zn2Ag3 trigonal bipyramids. In the third O site, O(3) is bonded in a square co-planar geometry to four equivalent Ag(1) atoms.