This work is an attempt to address the issue of metal-metal bonding in d¹⁰ systems. The compound [Ag(dmtp)NO₃]₂, where dmtp represents the ligand 5,7-dimethyl (1,2,4) triazolo (1,5- α) pyrimidine has been prepared, characterized by thermal analysis and IR spectroscopy and its structure has been solved by X-ray diffraction. The compound is triclinic, space group Pî , a = 5.1295(4), b = 9.6009(7), c = 10.332(2) Å, α = 103.73(1), β = 99.14(1), γ = 97.67(1)º, Z = 2, D_cal = 2.200 g cm^-3, R = 0.029 for 4144 observed reflections. The compound exhibits a [Ag₂(dmtp)₂]²⁺ core structure with two silver atoms bridged by the dmtp ligands via N3 and N4 to give eight-membered Ag₂N₄C₂ rings. The nitrate groups are coordinated in a semibridging and semichelating way (distances Ag-O, 2.816(2) Angstrom for non-bridging and 2.653(2) and 2.749(2) Å for bridging oxygens). The Ag-Ag separation is 3.058(1) Å, only 0.17 Å greater than in metallic silver. In order to make checking of the possible Ag-Ag bonding, a theoretical analysis has been performed, based on the properties of the charge density distribution derived from ab initio MO calculations using STO-3G* and 3-21G(*) wavefunctions, a significant direction interaction between the two metal centres having been found. Similar conclusions have been obtained for the model compound [Ag(NHCHNH)]₂ after performing a geometry optimization and using improved LANL2DZ wavefunctions that take into account relativistic effect.