Two new silver(I)-saccharinato (sac) complexes, [Ag(sac)(dmamhpy)] (1), [Ag-2(sac)(2)(aeprd)(2)] (2), (dmamhpy = 2-(dimethylaminomethyl)-3-hydroxypyridine and aeprd =N-(2-aminoethyl)pyrrolidine, have been prepared and characterized by elemental analysis, IR spectroscopy, thermal analysis and single crystal X-ray diffraction. X-ray diffraction analyses reveal that complexes 1 and 2 have a dimeric structure containing three-coordinate silver(I) ions with a distorted T-shaped coordination of AgN3. The dimeric structure of complex 1 is achieved by aromatic pi...pi stacking interactions, while the dimeric structure of complex 2 was governed by ligand unsupported Ag...Ag interaction with Ag-Ag contact of 3.1444(3) angstrom. The dimeric units are further linked by hydrogen bonds and C-H...pi interactions into a three-dimensional supramolecular network so that the structure of 1 has solvent accessible voids with a volume of 132.1 angstrom(3). IR spectra and thermal analysis data for 1 and 2 are in agreement with the crystal structures. Complex 2 displays intense luminescence with emission maximum at 373 nm upon excitation at 2 10 nm. On the basis of experiment, both complexes were calculated by DFT-B3LYP/3-21G in GAUSSIAN 03. (c) 2006 Elsevier B.V. All rights reserved.