NaAg(SO2)2 crystallizes in the monoclinic Pc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(3), one O(4), one O(6), and one O(7) atom to form corner-sharing NaO5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 69-71°. In the second Na site, Na(2) is bonded to one O(1), one O(4), one O(5), one O(8), and two equivalent O(2) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Na(1)O5 trigonal bipyramids, and  a cornercorner with one Ag(2)S3O trigonal pyramid. The corner-sharing octahedral tilt angles are 65°. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 1-coordinate geometry to one S(1), two equivalent S(2), and one O(7) atom. In the second Ag site, Ag(2) is bonded to one S(2), two equivalent S(1), and one O(8) atom to form distorted AgS3O trigonal pyramids that share  a cornercorner with one Na(2)O6 octahedra and corners with two equivalent Ag(2)S3O trigonal pyramids. The corner-sharing octahedral tilt angles are 63°. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Ag(1), two equivalent Ag(2), and one S(3) atom to form distorted corner-sharing SAg3S trigonal pyramids. In the second S site, S(2) is bonded to one Ag(2), two equivalent Ag(1), and one S(4) atom to form distorted corner-sharing SAg3S tetrahedra. In the third S site, S(3) is bonded in a trigonal non-coplanar geometry to one S(1), one O(1), one O(2), and one O(3) atom. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one S(2), one O(4), one O(5), and one O(6) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Na(2), and one S(3) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Na(2) and one S(3) atom. In the third O site, O(3) is bonded in a linear geometry to one Na(1) and one S(3) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Na(1), one Na(2), and one S(4) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Na(2) and one S(4) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one S(4) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one Ag(1) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Na(2) and one Ag(2) atom.
NaAg(SO2)2 crystallizes in the monoclinic Pc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(3), one O(4), one O(6), and one O(7) atom to form corner-sharing NaO5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 69-71°. The Na(1)-O(1) bond length is 2.35 Å. The Na(1)-O(3) bond length is 2.33 Å. The Na(1)-O(4) bond length is 2.40 Å. The Na(1)-O(6) bond length is 2.39 Å. The Na(1)-O(7) bond length is 2.44 Å. In the second Na site, Na(2) is bonded to one O(1), one O(4), one O(5), one O(8), and two equivalent O(2) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Na(1)O5 trigonal bipyramids, and  a cornercorner with one Ag(2)S3O trigonal pyramid. The corner-sharing octahedral tilt angles are 65°. The Na(2)-O(1) bond length is 2.56 Å. The Na(2)-O(4) bond length is 2.41 Å. The Na(2)-O(5) bond length is 2.34 Å. The Na(2)-O(8) bond length is 2.44 Å. There is one shorter (2.38 Å) and one longer (2.58 Å) Na(2)-O(2) bond length. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 1-coordinate geometry to one S(1), two equivalent S(2), and one O(7) atom. The Ag(1)-S(1) bond length is 2.54 Å. There is one shorter (2.61 Å) and one longer (2.72 Å) Ag(1)-S(2) bond length. The Ag(1)-O(7) bond length is 2.08 Å. In the second Ag site, Ag(2) is bonded to one S(2), two equivalent S(1), and one O(8) atom to form distorted AgS3O trigonal pyramids that share  a cornercorner with one Na(2)O6 octahedra and corners with two equivalent Ag(2)S3O trigonal pyramids. The corner-sharing octahedral tilt angles are 63°. The Ag(2)-S(2) bond length is 2.53 Å. There is one shorter (2.52 Å) and one longer (2.72 Å) Ag(2)-S(1) bond length. The Ag(2)-O(8) bond length is 2.09 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Ag(1), two equivalent Ag(2), and one S(3) atom to form distorted corner-sharing SAg3S trigonal pyramids. The S(1)-S(3) bond length is 2.16 Å. In the second S site, S(2) is bonded to one Ag(2), two equivalent Ag(1), and one S(4) atom to form distorted corner-sharing SAg3S tetrahedra. The S(2)-S(4) bond length is 2.15 Å. In the third S site, S(3) is bonded in a trigonal non-coplanar geometry to one S(1), one O(1), one O(2), and one O(3) atom. The S(3)-O(1) bond length is 1.47 Å. The S(3)-O(2) bond length is 1.47 Å. The S(3)-O(3) bond length is 1.46 Å. In the fourth S site, S(4) is bonded in a trigonal non-coplanar geometry to one S(2), one O(4), one O(5), and one O(6) atom. The S(4)-O(4) bond length is 1.47 Å. The S(4)-O(5) bond length is 1.46 Å. The S(4)-O(6) bond length is 1.47 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Na(2), and one S(3) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Na(2) and one S(3) atom. In the third O site, O(3) is bonded in a linear geometry to one Na(1) and one S(3) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Na(1), one Na(2), and one S(4) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Na(2) and one S(4) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one S(4) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one Ag(1) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Na(2) and one Ag(2) atom.