Mg(AgO2)2 crystallizes in the orthorhombic Cmcm space group. Mg(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. 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 0-66°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Mg(1) and three equivalent Ag(1) atoms to form distorted OMg2Ag3 trigonal bipyramids that share corners with five equivalent O(2)Mg2Ag2 tetrahedra, corners with two equivalent O(1)Mg2Ag3 trigonal bipyramids,  an edgeedge with one O(2)Mg2Ag2 tetrahedra, and edges with five equivalent O(1)Mg2Ag3 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Mg(1) and two equivalent Ag(1) atoms to form OMg2Ag2 tetrahedra that share corners with two equivalent O(2)Mg2Ag2 tetrahedra, corners with ten equivalent O(1)Mg2Ag3 trigonal bipyramids, and edges with two equivalent O(1)Mg2Ag3 trigonal bipyramids. In the third O site, O(3) is bonded in a distorted square co-planar geometry to four equivalent Ag(1) atoms.
Mg(AgO2)2 crystallizes in the orthorhombic Cmcm space group. Mg(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Both Mg(1)-O(2) bond lengths are 2.11 Å. All Mg(1)-O(1) bond lengths are 2.28 Å. 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 0-66°. The Ag(1)-O(2) bond length is 2.08 Å. Both Ag(1)-O(3) bond lengths are 2.21 Å. There is one shorter (2.10 Å) and two longer (2.33 Å) Ag(1)-O(1) bond lengths. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Mg(1) and three equivalent Ag(1) atoms to form distorted OMg2Ag3 trigonal bipyramids that share corners with five equivalent O(2)Mg2Ag2 tetrahedra, corners with two equivalent O(1)Mg2Ag3 trigonal bipyramids,  an edgeedge with one O(2)Mg2Ag2 tetrahedra, and edges with five equivalent O(1)Mg2Ag3 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Mg(1) and two equivalent Ag(1) atoms to form OMg2Ag2 tetrahedra that share corners with two equivalent O(2)Mg2Ag2 tetrahedra, corners with ten equivalent O(1)Mg2Ag3 trigonal bipyramids, and edges with two equivalent O(1)Mg2Ag3 trigonal bipyramids. In the third O site, O(3) is bonded in a distorted square co-planar geometry to four equivalent Ag(1) atoms.