Zn(AgO2)2 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Ag sites. In the first Ag site, Ag(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 AgO6 octahedra. The corner-sharing octahedral tilt angles range from 48-71°. In the second Ag site, Ag(2) is bonded to one O(2), two equivalent O(4), and three equivalent O(1) atoms to form a mixture of distorted edge and corner-sharing AgO6 octahedra. The corner-sharing octahedral tilt angles range from 48-71°. 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 in a 5-coordinate geometry to three equivalent Ag(2) and two equivalent Zn(1) atoms. In the second O site, O(2) is bonded to one Ag(2), two equivalent Ag(1), and one Zn(1) atom to form distorted OZnAg3 trigonal pyramids that share corners with two equivalent O(4)Zn2Ag3 trigonal bipyramids, corners with six equivalent O(3)Zn2Ag3 trigonal bipyramids, corners with two equivalent O(2)ZnAg3 trigonal pyramids,  an edgeedge with one O(3)Zn2Ag3 trigonal bipyramid, and edges with two equivalent O(4)Zn2Ag3 trigonal bipyramids. In the third O site, O(3) 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(4)Zn2Ag3 trigonal bipyramids, corners with six equivalent O(2)ZnAg3 trigonal pyramids,  an edgeedge with one O(4)Zn2Ag3 trigonal bipyramid, edges with four equivalent O(3)Zn2Ag3 trigonal bipyramids, and  an edgeedge with one O(2)ZnAg3 trigonal pyramid. In the fourth O site, O(4) is bonded to one Ag(1), two equivalent Ag(2), and two equivalent Zn(1) atoms to form distorted OZn2Ag3 trigonal bipyramids that share corners with five equivalent O(3)Zn2Ag3 trigonal bipyramids, corners with two equivalent O(2)ZnAg3 trigonal pyramids,  an edgeedge with one O(3)Zn2Ag3 trigonal bipyramid, edges with two equivalent O(4)Zn2Ag3 trigonal bipyramids, and edges with two equivalent O(2)ZnAg3 trigonal pyramids.
Zn(AgO2)2 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Ag sites. In the first Ag site, Ag(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 AgO6 octahedra. The corner-sharing octahedral tilt angles range from 48-71°. The Ag(1)-O(4) bond length is 2.14 Å. Both Ag(1)-O(2) bond lengths are 2.09 Å. There is one shorter (2.14 Å) and two longer (2.22 Å) Ag(1)-O(3) bond lengths. In the second Ag site, Ag(2) is bonded to one O(2), two equivalent O(4), and three equivalent O(1) atoms to form a mixture of distorted edge and corner-sharing AgO6 octahedra. The corner-sharing octahedral tilt angles range from 48-71°. The Ag(2)-O(2) bond length is 2.04 Å. Both Ag(2)-O(4) bond lengths are 2.43 Å. There is one shorter (2.11 Å) and two longer (2.51 Å) Ag(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 2.45 Å. Both Zn(1)-O(1) bond lengths are 2.12 Å. Both Zn(1)-O(3) bond lengths are 2.51 Å. Both Zn(1)-O(4) bond lengths are 2.16 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to three equivalent Ag(2) and two equivalent Zn(1) atoms. In the second O site, O(2) is bonded to one Ag(2), two equivalent Ag(1), and one Zn(1) atom to form distorted OZnAg3 trigonal pyramids that share corners with two equivalent O(4)Zn2Ag3 trigonal bipyramids, corners with six equivalent O(3)Zn2Ag3 trigonal bipyramids, corners with two equivalent O(2)ZnAg3 trigonal pyramids,  an edgeedge with one O(3)Zn2Ag3 trigonal bipyramid, and edges with two equivalent O(4)Zn2Ag3 trigonal bipyramids. In the third O site, O(3) 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(4)Zn2Ag3 trigonal bipyramids, corners with six equivalent O(2)ZnAg3 trigonal pyramids,  an edgeedge with one O(4)Zn2Ag3 trigonal bipyramid, edges with four equivalent O(3)Zn2Ag3 trigonal bipyramids, and  an edgeedge with one O(2)ZnAg3 trigonal pyramid. In the fourth O site, O(4) is bonded to one Ag(1), two equivalent Ag(2), and two equivalent Zn(1) atoms to form distorted OZn2Ag3 trigonal bipyramids that share corners with five equivalent O(3)Zn2Ag3 trigonal bipyramids, corners with two equivalent O(2)ZnAg3 trigonal pyramids,  an edgeedge with one O(3)Zn2Ag3 trigonal bipyramid, edges with two equivalent O(4)Zn2Ag3 trigonal bipyramids, and edges with two equivalent O(2)ZnAg3 trigonal pyramids.