MgZn2(AgO2)4 crystallizes in the orthorhombic Amm2 space group. Mg(1) is bonded in a distorted trigonal planar geometry to one O(4) and two equivalent O(2) atoms. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(1), and two equivalent O(5) atoms. In the second Ag site, Ag(2) is bonded in a 6-coordinate geometry to one O(1), one O(4), two equivalent O(2), and two equivalent O(5) atoms. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(2) and two equivalent O(4) atoms to form corner-sharing ZnO4 tetrahedra. In the second Zn site, Zn(2) is bonded in a see-saw-like geometry to two equivalent O(3) and two equivalent O(5) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Ag(2), two equivalent Ag(1), and one O(1) atom. In the second O site, O(2) is bonded to one Mg(1), one Ag(1), two equivalent Ag(2), and one Zn(1) atom to form OMgZnAg3 trigonal bipyramids that share  a cornercorner with one O(3)Zn2Ag2 tetrahedra, corners with two equivalent O(2)MgZnAg3 trigonal bipyramids, and  an edgeedge with one O(2)MgZnAg3 trigonal bipyramid. In the third O site, O(3) is bonded to two equivalent Ag(1) and two equivalent Zn(2) atoms to form distorted OZn2Ag2 tetrahedra that share corners with two equivalent O(3)Zn2Ag2 tetrahedra and corners with two equivalent O(2)MgZnAg3 trigonal bipyramids. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mg(1), two equivalent Ag(2), and two equivalent Zn(1) atoms. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to two equivalent Ag(1), two equivalent Ag(2), and one Zn(2) atom.
MgZn2(AgO2)4 crystallizes in the orthorhombic Amm2 space group. Mg(1) is bonded in a distorted trigonal planar geometry to one O(4) and two equivalent O(2) atoms. The Mg(1)-O(4) bond length is 1.91 Å. Both Mg(1)-O(2) bond lengths are 1.95 Å. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(1), and two equivalent O(5) atoms. The Ag(1)-O(2) bond length is 2.32 Å. The Ag(1)-O(3) bond length is 2.16 Å. Both Ag(1)-O(1) bond lengths are 2.60 Å. Both Ag(1)-O(5) bond lengths are 2.61 Å. In the second Ag site, Ag(2) is bonded in a 6-coordinate geometry to one O(1), one O(4), two equivalent O(2), and two equivalent O(5) atoms. The Ag(2)-O(1) bond length is 2.57 Å. The Ag(2)-O(4) bond length is 2.75 Å. Both Ag(2)-O(2) bond lengths are 2.36 Å. Both Ag(2)-O(5) bond lengths are 2.19 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(2) and two equivalent O(4) atoms to form corner-sharing ZnO4 tetrahedra. Both Zn(1)-O(2) bond lengths are 2.13 Å. Both Zn(1)-O(4) bond lengths are 1.98 Å. In the second Zn site, Zn(2) is bonded in a see-saw-like geometry to two equivalent O(3) and two equivalent O(5) atoms. Both Zn(2)-O(3) bond lengths are 1.97 Å. Both Zn(2)-O(5) bond lengths are 2.04 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Ag(2), two equivalent Ag(1), and one O(1) atom. The O(1)-O(1) bond length is 1.29 Å. In the second O site, O(2) is bonded to one Mg(1), one Ag(1), two equivalent Ag(2), and one Zn(1) atom to form OMgZnAg3 trigonal bipyramids that share  a cornercorner with one O(3)Zn2Ag2 tetrahedra, corners with two equivalent O(2)MgZnAg3 trigonal bipyramids, and  an edgeedge with one O(2)MgZnAg3 trigonal bipyramid. In the third O site, O(3) is bonded to two equivalent Ag(1) and two equivalent Zn(2) atoms to form distorted OZn2Ag2 tetrahedra that share corners with two equivalent O(3)Zn2Ag2 tetrahedra and corners with two equivalent O(2)MgZnAg3 trigonal bipyramids. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mg(1), two equivalent Ag(2), and two equivalent Zn(1) atoms. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to two equivalent Ag(1), two equivalent Ag(2), and one Zn(2) atom.