Mg(AgO2)2 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. Mg(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MgO6 octahedra that share corners with six equivalent Ag(1)O4 tetrahedra, edges with two equivalent Mg(1)O6 octahedra, and edges with four equivalent Ag(2)O6 octahedra. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted AgO4 tetrahedra that share corners with six equivalent Mg(1)O6 octahedra and corners with six equivalent Ag(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-80°. In the second Ag site, Ag(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form AgO6 octahedra that share corners with six equivalent Ag(1)O4 tetrahedra, edges with two equivalent Ag(2)O6 octahedra, and edges with four equivalent Mg(1)O6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Mg(1), one Ag(1), and one Ag(2) atom to form OMg2Ag2 trigonal pyramids that share corners with six equivalent O(1)Mg2Ag2 trigonal pyramids, corners with six equivalent O(2)MgAg3 trigonal pyramids,  an edgeedge with one O(1)Mg2Ag2 trigonal pyramid, and edges with two equivalent O(2)MgAg3 trigonal pyramids. In the second O site, O(2) is bonded to one Mg(1), one Ag(1), and two equivalent Ag(2) atoms to form OMgAg3 trigonal pyramids that share corners with six equivalent O(1)Mg2Ag2 trigonal pyramids, corners with six equivalent O(2)MgAg3 trigonal pyramids,  an edgeedge with one O(2)MgAg3 trigonal pyramid, and edges with two equivalent O(1)Mg2Ag2 trigonal pyramids.
Mg(AgO2)2 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. Mg(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MgO6 octahedra that share corners with six equivalent Ag(1)O4 tetrahedra, edges with two equivalent Mg(1)O6 octahedra, and edges with four equivalent Ag(2)O6 octahedra. Both Mg(1)-O(2) bond lengths are 2.13 Å. All Mg(1)-O(1) bond lengths are 2.11 Å. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted AgO4 tetrahedra that share corners with six equivalent Mg(1)O6 octahedra and corners with six equivalent Ag(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-80°. Both Ag(1)-O(1) bond lengths are 2.16 Å. Both Ag(1)-O(2) bond lengths are 2.21 Å. In the second Ag site, Ag(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form AgO6 octahedra that share corners with six equivalent Ag(1)O4 tetrahedra, edges with two equivalent Ag(2)O6 octahedra, and edges with four equivalent Mg(1)O6 octahedra. Both Ag(2)-O(1) bond lengths are 2.07 Å. All Ag(2)-O(2) bond lengths are 2.15 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Mg(1), one Ag(1), and one Ag(2) atom to form OMg2Ag2 trigonal pyramids that share corners with six equivalent O(1)Mg2Ag2 trigonal pyramids, corners with six equivalent O(2)MgAg3 trigonal pyramids,  an edgeedge with one O(1)Mg2Ag2 trigonal pyramid, and edges with two equivalent O(2)MgAg3 trigonal pyramids. In the second O site, O(2) is bonded to one Mg(1), one Ag(1), and two equivalent Ag(2) atoms to form OMgAg3 trigonal pyramids that share corners with six equivalent O(1)Mg2Ag2 trigonal pyramids, corners with six equivalent O(2)MgAg3 trigonal pyramids,  an edgeedge with one O(2)MgAg3 trigonal pyramid, and edges with two equivalent O(1)Mg2Ag2 trigonal pyramids.