Silver Coodination Polymers with Flexible Ligands. Syntheses, Crystal Structures, and Effect of the Counteranion and the Solvent on the Structure of Complexes [Ag<b>L</b>X]_∞ of the Bis(Phenylthio)methane Ligand <b>L</b><b>¹</b> 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, ClO 4 - ( 1 ) and BF 4 - ( 2 ), as well as two slightly “elongated” ones, CF 3 COO - ( 3 ) and CF 3 SO 3 - ( 4, 5 ). Complexes with a longer anion, CF 3 CF 2 CF 2 COO - ( 6 ), and a diacid, - OOCCF 2 CF 2 COO - ( 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−] ∞ 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 CF 3 SO 3 - 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, Ag 4 L 1 4, was noted when petroleum ether was used, 5 . The macrocycles are connected through a small cyclic (CF 3 SO 3 ···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 Ag 4 L 1 2 macrocycle. In compound 7, with the tetrafluorosuccinate anion, one observes another type of 1D-polymer best described as a [Ag 2 −tetrafluorosuccinate−] ∞ 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 Å) that correlate with an FTIR absorption band around 521 cm -1 . Relatively short Ag···Ag interactions are found in both 6 and 7 .

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