Abstract: | The structure of the title compound, polyμ3‐N′‐(3‐cyanobenzylidene)nicotinohydrazide]silver(I)] hexafluoroarsenate], {Ag(C14H10N4O)](AsF6)}n, at 173 K exhibits a novel stair‐like two‐dimensional layer and a three‐dimensional supramolecular framework through C—H...Ag hydrogen bonds. The AgI cation is coordinated by three N atoms and one O atom from N′‐(3‐cyanobenzylidene)nicotinohydrazide (L) ligands, resulting in a distorted tetrahedral coordination geometry. The organic ligand acts as a μ3‐bridging ligand through the pyridyl and carbonitrile N atoms and deviates from planarity in order to adapt to the coordination geometry. Two ligands bridge two AgI cations to construct a small 2+2 Ag2L2 ring. Four ligands bridge one AgI cation from each of four of these small rings to form a large grid. An interesting stair‐like two‐dimensional (3,6)‐net is formed through AgI metal centres acting as three‐connection nodes and through L molecules as tri‐linkage spacers. |