This work presents the synthesis and crystal structures of novel Ag(I) complexes based on 1,2-bis[4-chlorophenyl)imino]acenaphthene (4-Cl-C6H4-bian) and 1,2-bis[4-iodophenyl)imino]acenaphthene (4-I-C6H4-bian). The interaction of AgCF3SO3 with 4-Cl-C6H4-bian led to exclusively tetrahedral complex [Ag(4-Cl-C6H4-bian)2](CF3SO3) (1) in a 90 % yield. In contrast, the same reaction with 4-I-C6H4-bian led to the formation of both tetrahedral complex [Ag(4-I-C6H4-bian)2](CF3SO3) (2) and unexpected binuclear complex [Ag2(µ-4-I-C6H4-bian)2(4-I-C6H4-NH2)2](CF3SO3)2 (3), in which 4-I-C6H4-bian acts as a bridging ligand linking two Ag(I) ions via N- and I-donor atoms. X-ray diffraction analysis revealed an anomalously long Ag-I distance (3.0833(3) Å) in 3, resulting in duality in determining the coordination mode of the Ag(I) ion. This could be a trigonal geometry (AgN3, CN = 3) or a strongly distorted trigonal-pyramidal [3+1] coordination (AgN3I, CN = 4). To establish the nature of the metal-ligand interactions in complexes 1-3 and determine the coordination number of Ag(I) in complex 3, a comprehensive theoretical study (DFT calculations) was carried out using four molecular descriptors: quantum theory of atoms in molecules (QTAIM), electron localization function (ELF), interacting quantum atoms (IQA) and second-order perturbation theory analysis of the natural bond orbital (NBO).