The system AgNO3 and L (L = ethanediyl bis(isonicotinate)) yielded so far five different compounds from a THF/H2O mixture (or acetonitrile) when reacted in a ratio 1:1. Three solvent-free compounds possess the same chemical composition, [Ag(L)NO3], but different structures and thus different properties. Additionally, two solvates [Ag(L)NO3] · nH2O with one or two water molecules have been identified. One of the solvates can be reversibly transformed into one of the solvent free compounds. This clay-like property depends strongly on the structure observed in the solid state, namely on the coordinating function of the nitrate ions with respect to silver cations. © 2006 Elsevier B.V. All rights reserved.