A staggered arrangement like that of the hydrogen atoms in ethane is exhibited by the six phenol groups about each pair of silver atoms in the self-assembled three-dimensional coordination networks [Ag₂(H₂L)₃]nX(2n) (H₂L = N,N'-bis-(salicylidene)-1,4-diaminobutane; X^- = NO₃^- or ClO₄^-); the former is depicted (for clarity the H₂L ligands are represented by long rods and the Ag atoms by hatched circles). These solids contain short ligand- unsupported metal-metal bonds and display intense blue photoluminescence at room temperature.