Influence of the counteranion on silver(I)–dithioether coordination polymers

In order to rationalize the effect of the size and coordinating ability of counteranions upon the structure of Ag(I)–dithioether coordination polymers, a series of such polymers has been synthesized by the combination of the 1,3-bis(methylthio)propane building block and AgX silver salts (X = ClO4− (1), BF4− (2), CF3SO3− (3), SbF6− (4), C6H5COO− (5), CF3COO− (6), CF3CF2CF2COO− (7) and −OOCCF2CF2COO− (8)). Except in two cases, all complexes form 1D-coordination polymers.Coordination polymers 1 and 2 are isostructural with tubular cationic chains. Coordination polymers 3 and 4 have similar cationic chains, except that 3 incorporates in its crystal structure an additional acetone molecule. In 5, neighboring [(C6H5COO)Ag]2 dimers are linked via the oxygen atom of the benzoate group to build up a [(C6H5COO)Ag]∞ 1D-dimensional coordination polymer. The chains are further interconnected by ligand molecules that bind two consecutive silver atoms.The short Ag⋯Ag contacts (2.920(1)–3.363(1) Å) in 5, 7 and 8 may indicate the presence of weak silver–silver interactions. Coordination polymer 6 forms a neutral 2D-coordination network, in which the trifluoroacetate anions complete the coordination sphere of the metal center. In 7, the neutral 1D-coordination polymer is made up through unsupported silver–silver interactions. The structure of 8 is made up of the same chains of 7 that are connected to each other by the tetrafluorosuccinate anions, resulting in a 2D-supramolecular network. The stoichiometries of polymers 1 and 2 were found to depend on the metal-to-ligand ratio of the starting materials, contrary to the stoichiometries of the other coordination networks 3–8.

Graphical abstractEight new silver(I) coordination polymers have been obtained from the self-assembly of 1,3-bis(methylthio)propane and AgX silver salts with different coordinating counteranions (X = ClO4− (1), BF4− (2), CF3SO3− (3), SbF6− (4), C6H5COO− (5), CF3COO− (6), CF3CF2CF2COO− (7) and −OOCCF2CF2COO− (8)). 1D and 2D coordination networks were made up through unsupported silver–silver interactions.Figure optionsDownload full-size imageDownload as PowerPoint slide