Silver coordination polymers with remarkably high packing coefficients

Abstract

Silver meso- and rac-tartrate and silver squarate have been synthesized, and the crystal structure of a new polymorph of the latter is reported. Three reaction products of these silver salts with pyrazine have been obtained and structurally characterized: From silver squarate, a chain polymer with linear coordination of Ag(I) by two pyrazine ligands is formed, whereas the silver tartrates yield solids in which the inner coordination sites around the metal are only partially occupied by N donors; in contrast to expectation, oxygen coordination prevails. All the four new Ag(I) coordination compounds reported show high packing coefficients in the range between 0.789 and 0.885. In order to put these results into a meaningful context, packing coefficients for the crystal structures of almost 30,000 compounds retrieved from the Cambridge Structural Database have been determined. Tartrates pack significantly closer than pyrazine complexes or metal-containing compounds in general. The exceptionally high packing coefficient of the new polymorph of silver squarate is due to stacking of anions and concomitant Ag···Ag contacts, both along the shortest lattice parameter which amounts to only 3.3990(9) A.