The reaction of silver nitrate with sodium saccharinate (Na[sac]) in the presence of 2-pyridinepropanol in aqueous solution yields the title complex, Na[Ag(sac)(2)]. The compound crystallizes in the triclinic space group P (1) over bar [a = 8.0481(6), b = 9.0587(6), c = 11.1642(8)Angstrom; alpha = 100.064(3), beta = 99.917(3) and gamma = 92.367(3)degrees Z = 2]. The structure consists of Na+ and [Ag(saC)(2)](-) ions, in which each silver(I) ion is doubly bridged by the sac ligands, exhibiting a distorted 'T' shaped AgN2O coordination arrangement with one long [Ag-O-sulfonyl = 2.6390(10) Angstrom] and two shorter bonds [Ag-N = 2.1405(11) and 2.1570(11) Angstrom]. The coordination around silver(l) is trigonal planar and the N-Ag-N bond angle is 158.99(5)degrees. The Na+ ion is five-coordinate with two carbonyl and three sulfonyl O atoms of the adjacent sac ligands and acts as a bridge between [Ag(sac)(2)](-) units, resulting in a three-dimensional network. The i.r. spectra and thermal decomposition behaviour of Na[Ag(sac)(2)] are discussed in detail.