Five new ligands bearing terminal ethynide moieties attached via pendant arms to a naphthyl skeleton have been used in the synthesis of eight silver(l) complexes. In these compounds, the invariable appearance of the mu(4) and mu(5) ligation modes of the ethynide moiety reaffirms the general utility of the silver-ethynide supramolecular synthons R-C=-C superset of Ag-n and Ag-n subset of C C-R-C C superset of Ag-n (n = 4, 5) in coordination network assembly, even when the R group is conformationally flexible. Besides the silver-ethynyl and silver-aromatic interactions, several unconventional intermolecular interactions (argentophilicity, anion-pi, C-H center dot center dot center dot pi, and C N center dot center dot center dot pi) also make their appearance.