A three-dimensional silver(I)-saccharinato (sac) coordination polymer [Ag-2(mu-Sac)21,, has been synthesized and characterized by elemental analysis, IR and single crystal X-ray diffraction. The silver(I) ions are doubly bridged by the imino N and carbonyl O atoms of two sac ligands, leading to a dimer [Ag-2(mu-sac)(2)] with a very short Ag-Ag contact of 2.8622(6) angstrom. The dimeric units are linked by unique Ag-C-sac (eta(1)) bonds into two-dimensional ladder-like layers, which are further assembled into a three-dimensional network by weak Ag ...O(sulphonyl) and pi(sac) ... pi(sac) interactions. Complex 1 is the first example of a polymeric network involving the eta(1) Ag-C bonds. In addition to the new coordination mode of sac, the IR spectrum and thermal properties of the complex were discussed. (C) 2010 Elsevier B.V. All rights reserved.