Three pairs of complementary nitrogen heteroaryl ligands [2,6-(C C)(2)-py and 2-C C-pym; 2,5-(C C)(2)-py and 2-C C-pyz; 3,5-(C C)(2)-py and 5-C C-pym (py = pyridine, pyz = pyrazine, pym = pyrimidine)], wherein a ring nitrogen atom in one is interchanged with a carbon atom bearing an ethynyl substituent in the other, have been used to generate seven silver(I) complexes (1-7), in which silver infinite chains and two-dimensional coordination networks bridged by heteroaryl ethynide ligands were obtained as pre-programmed. The relative positions and bonding preference between the ethynide group and ring nitrogen atom act as controlling factors to produce various structural building units for the formation of multidimensional coordination networks, The fusion of C C superset of Ag-n (n = 3, 4) building units yields multinuclear silver aggregates in 1-6 whose nuclearities range from seven to twelve. The crystal structure of 7 displays a honeycomb layer composed of Ag-4 baskets alternately linked by pyrimidinyl-5-ethynide ligands. In addition, complex 1 features an infinite chain composed of an alternate arrangement of twist-boat water hexamers and bridging silver atoms.