MgSc2(AgO3)2 crystallizes in the orthorhombic Amm2 space group. Mg(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Sc(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of distorted edge and corner-sharing ScO6 octahedra. The corner-sharing octahedral tilt angles are 56°. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(3) atoms. In the second Ag site, Ag(2) is bonded in a 6-coordinate geometry to two equivalent O(3) and four equivalent O(2) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Mg(1), two equivalent Sc(1), and one Ag(1) atom to form distorted OMg2Sc2Ag trigonal bipyramids that share corners with two equivalent O(1)Mg2Sc2Ag trigonal bipyramids, corners with four equivalent O(3)Sc2Ag2 trigonal pyramids, edges with two equivalent O(1)Mg2Sc2Ag trigonal bipyramids,  an edgeedge with one O(3)Sc2Ag2 trigonal pyramid, and  a faceface with one O(1)Mg2Sc2Ag trigonal bipyramid. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Mg(1), two equivalent Sc(1), and two equivalent Ag(2) atoms. In the third O site, O(3) is bonded to two equivalent Sc(1), one Ag(1), and one Ag(2) atom to form OSc2Ag2 trigonal pyramids that share corners with four equivalent O(1)Mg2Sc2Ag trigonal bipyramids, corners with two equivalent O(3)Sc2Ag2 trigonal pyramids,  an edgeedge with one O(1)Mg2Sc2Ag trigonal bipyramid, and  an edgeedge with one O(3)Sc2Ag2 trigonal pyramid.
MgSc2(AgO3)2 crystallizes in the orthorhombic Amm2 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 2.12 Å. All Mg(1)-O(1) bond lengths are 2.29 Å. Sc(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of distorted edge and corner-sharing ScO6 octahedra. The corner-sharing octahedral tilt angles are 56°. Both Sc(1)-O(1) bond lengths are 2.24 Å. There is one shorter (2.11 Å) and one longer (2.47 Å) Sc(1)-O(2) bond length. Both Sc(1)-O(3) bond lengths are 2.04 Å. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(3) atoms. Both Ag(1)-O(1) bond lengths are 2.09 Å. Both Ag(1)-O(3) bond lengths are 2.07 Å. In the second Ag site, Ag(2) is bonded in a 6-coordinate geometry to two equivalent O(3) and four equivalent O(2) atoms. Both Ag(2)-O(3) bond lengths are 2.41 Å. All Ag(2)-O(2) bond lengths are 2.39 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Mg(1), two equivalent Sc(1), and one Ag(1) atom to form distorted OMg2Sc2Ag trigonal bipyramids that share corners with two equivalent O(1)Mg2Sc2Ag trigonal bipyramids, corners with four equivalent O(3)Sc2Ag2 trigonal pyramids, edges with two equivalent O(1)Mg2Sc2Ag trigonal bipyramids,  an edgeedge with one O(3)Sc2Ag2 trigonal pyramid, and  a faceface with one O(1)Mg2Sc2Ag trigonal bipyramid. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Mg(1), two equivalent Sc(1), and two equivalent Ag(2) atoms. In the third O site, O(3) is bonded to two equivalent Sc(1), one Ag(1), and one Ag(2) atom to form OSc2Ag2 trigonal pyramids that share corners with four equivalent O(1)Mg2Sc2Ag trigonal bipyramids, corners with two equivalent O(3)Sc2Ag2 trigonal pyramids,  an edgeedge with one O(1)Mg2Sc2Ag trigonal bipyramid, and  an edgeedge with one O(3)Sc2Ag2 trigonal pyramid.