Silver coodination polymers with flexible ligands.: Syntheses, crystal structures, and effect of the counteranion and the solvent on the structure of complexes [AgL1X]∞ of the bis(phenylthio)methane ligand L1 with silver(I) salts, X = ClO4-, BF4-, CF3COO-, CF3SO3-, CF3CF2CF2COO-, and -OOCCF2CF2COO-

A number of complexes were synthesized to rationalize the structures of Ag(I) complexes with a small flexible bidentate ligand, bis(phenylthio)methane, when the anion is varied. We compared two similar "spherical" anions, ClO4- (1) and BF4- (2), as well as two slightly "elongated" ones, CF3COO- (3) and CF3SO3- (4, 5). Complexes with a longer anion, CF3CF2CF2COO- (6), and a diacid, -OOCCF2CF2COO- (7), were also investigated. All the compounds studied form a 1D-coordination polymer. The coordination polymers of 1-4 are of the type [Ag-ligand-](infinity) and adopt two distinct conformations: gauche-trans-gauche for 1, 2, and 4, and gauche-gauche-gauche for 3. The anions in 1-4 are coordinated to the silver atoms through a single O or F atom. All these 1D-chains are associated through weak van der Waals interactions into 2D-layer structures. Solvent-induced supramolecular isomerism was observed with the CF3SO3- anion. With diethyl ether, the 1D-coordination polymer of 4 was observed, as indicated above, while a two-stranded chain comprising a 16-membered macrocyclic structure, Ag4L41, was noted when petroleum ether was used, 5. The macrocycles are connected through a small cyclic ((CF3SO3Ag...)-Ag-...)(2) dimeric unit. Another type of double-stranded ladder-like structure was noted for 6. Each of the two heptafluorobutyrate anions is coordinated through its oxygen atoms to two distinct silver atoms to form a dimeric unit. This, in turn, is connected to another unit through two Ag-S coordination bonds. The repeat unit of this coordination polymer is based on a 10-membered Ag4L21 macrocycle. In compound 7, with the tetrafluorosuccinate anion, one observes another type of 1D-polymer best described as a [Ag-2-tetrafluorosuccinate-](infinity) chain reinforced by Ag-ligand-Ag bonds. Most complexes containing fluorine atoms have C(H)F-... or C(H-2)F-... short contacts (2.998-3.203 angstrom) that correlate with an FTIR absorption band around 521 cm(-1). Relatively short (AgAg)-Ag-... interactions are found in both 6 and 7.