Ba(Ag3O2)2 crystallizes in the orthorhombic Pnna space group. Ba(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form edge-sharing BaO6 octahedra. There are four inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a linear geometry to one O(1) and one O(2) atom. In the second Ag site, Ag(2) is bonded in a linear geometry to one O(1) and one O(2) atom. In the third Ag site, Ag(3) is bonded in a bent 120 degrees geometry to two equivalent O(2) atoms. In the fourth Ag site, Ag(4) is bonded in a linear geometry to two equivalent O(1) atoms. There are two inequivalent O sites. In the first O site, O(2) is bonded to two equivalent Ba(1), one Ag(1), one Ag(2), and one Ag(3) atom to form OBa2Ag3 trigonal bipyramids that share corners with five equivalent O(2)Ba2Ag3 trigonal bipyramids, corners with six equivalent O(1)BaAg3 trigonal pyramids, and  an edgeedge with one O(2)Ba2Ag3 trigonal bipyramid. In the second O site, O(1) is bonded to one Ba(1), one Ag(1), one Ag(2), and one Ag(4) atom to form distorted OBaAg3 trigonal pyramids that share corners with six equivalent O(2)Ba2Ag3 trigonal bipyramids and corners with two equivalent O(1)BaAg3 trigonal pyramids.
Ba(Ag3O2)2 crystallizes in the orthorhombic Pnna space group. Ba(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form edge-sharing BaO6 octahedra. Both Ba(1)-O(1) bond lengths are 2.63 Å. There are two shorter (2.62 Å) and two longer (2.88 Å) Ba(1)-O(2) bond lengths. There are four inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a linear geometry to one O(1) and one O(2) atom. The Ag(1)-O(1) bond length is 2.10 Å. The Ag(1)-O(2) bond length is 2.08 Å. In the second Ag site, Ag(2) is bonded in a linear geometry to one O(1) and one O(2) atom. The Ag(2)-O(1) bond length is 2.06 Å. The Ag(2)-O(2) bond length is 2.07 Å. In the third Ag site, Ag(3) is bonded in a bent 120 degrees geometry to two equivalent O(2) atoms. Both Ag(3)-O(2) bond lengths are 2.35 Å. In the fourth Ag site, Ag(4) is bonded in a linear geometry to two equivalent O(1) atoms. Both Ag(4)-O(1) bond lengths are 2.08 Å. There are two inequivalent O sites. In the first O site, O(2) is bonded to two equivalent Ba(1), one Ag(1), one Ag(2), and one Ag(3) atom to form OBa2Ag3 trigonal bipyramids that share corners with five equivalent O(2)Ba2Ag3 trigonal bipyramids, corners with six equivalent O(1)BaAg3 trigonal pyramids, and  an edgeedge with one O(2)Ba2Ag3 trigonal bipyramid. In the second O site, O(1) is bonded to one Ba(1), one Ag(1), one Ag(2), and one Ag(4) atom to form distorted OBaAg3 trigonal pyramids that share corners with six equivalent O(2)Ba2Ag3 trigonal bipyramids and corners with two equivalent O(1)BaAg3 trigonal pyramids.