NaAg(NO2)2 crystallizes in the orthorhombic Fdd2 space group. Na(1) is bonded to one N(1), two equivalent O(2), and four equivalent O(1) atoms to form distorted corner-sharing NaNO6 pentagonal bipyramids. Ag(1) is bonded in a 7-coordinate geometry to one N(2), two equivalent O(1), and four equivalent O(2) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Na(1) and two equivalent O(2) atoms. In the second N site, N(2) is bonded in a trigonal planar geometry to one Ag(1) and two equivalent O(1) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ag(1), and one N(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), two equivalent Ag(1), and one N(1) atom.
NaAg(NO2)2 crystallizes in the orthorhombic Fdd2 space group. Na(1) is bonded to one N(1), two equivalent O(2), and four equivalent O(1) atoms to form distorted corner-sharing NaNO6 pentagonal bipyramids. The Na(1)-N(1) bond length is 2.58 Å. Both Na(1)-O(2) bond lengths are 2.42 Å. There are two shorter (2.40 Å) and two longer (2.51 Å) Na(1)-O(1) bond lengths. Ag(1) is bonded in a 7-coordinate geometry to one N(2), two equivalent O(1), and four equivalent O(2) atoms. The Ag(1)-N(2) bond length is 2.20 Å. Both Ag(1)-O(1) bond lengths are 2.70 Å. There are two shorter (2.41 Å) and two longer (2.82 Å) Ag(1)-O(2) bond lengths. There are two inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Na(1) and two equivalent O(2) atoms. Both N(1)-O(2) bond lengths are 1.26 Å. In the second N site, N(2) is bonded in a trigonal planar geometry to one Ag(1) and two equivalent O(1) atoms. Both N(2)-O(1) bond lengths are 1.26 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ag(1), and one N(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), two equivalent Ag(1), and one N(1) atom.