NaH2(SO2)2 crystallizes in the monoclinic C2 space group. Na(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted face-sharing NaO6 octahedra. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(4) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(4) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded in a water-like geometry to one S(1) and one S(2) atom. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to one S(1), one O(1), one O(2), and one O(3) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one S(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one S(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one S(2) atom. In the fourth O site, O(4) is bonded in a distorted water-like geometry to two equivalent Na(1), one H(1), and one H(2) atom.
NaH2(SO2)2 crystallizes in the monoclinic C2 space group. Na(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted face-sharing NaO6 octahedra. There is one shorter (2.38 Å) and one longer (2.51 Å) Na(1)-O(2) bond length. There is one shorter (2.40 Å) and one longer (2.42 Å) Na(1)-O(3) bond length. There is one shorter (2.39 Å) and one longer (2.45 Å) Na(1)-O(4) bond length. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(4) atom. The H(1)-O(4) bond length is 0.98 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(4) atom. The H(2)-O(4) bond length is 0.98 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a water-like geometry to one S(1) and one S(2) atom. The S(1)-S(1) bond length is 2.01 Å. The S(1)-S(2) bond length is 2.19 Å. In the second S site, S(2) 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(2)-O(1) bond length is 1.47 Å. The S(2)-O(2) bond length is 1.47 Å. The S(2)-O(3) bond length is 1.47 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one S(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one S(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one S(2) atom. In the fourth O site, O(4) is bonded in a distorted water-like geometry to two equivalent Na(1), one H(1), and one H(2) atom.