One-Dimensional Coordination Polymers Incorporating Silver(I) Perfluorocarboxylate Cuboctahedral Clusters and the Bis(methylthio)methane Ligand

Two topologically comparable complexes, [Ag₆(CF₃CO₂)₃(L^1-Me)₃(SCH₃)₃]_∞ (1) and [Ag₆(CF₃CF₂CO₂)₃(L^1-Me)₂(SCH₃)₃(H₂O)]_∞ (2), were prepared and characterized by single-crystal diffractometry. The structures consist of Ag₁₂S₆ clusters linked by bis(methylthio)methane ligands, L^1-Me, thus forming 1D coordination polymers. The 12 Ag atoms of the cluster are situated at the corners of a distorted cuboctahedron. The sulfur atoms of the six μ₄-SCH₃ entities occupy a position ∼0.8 Å above the center of each of the square faces of the polyhedron. The cleavage of the C−S bond of some of the ligands occurs during the syntheses, producing the ^-SCH₃ anions. The coordination of the silver atoms varies from 5 to 7. The Ag···Ag contacts range from 2.9250(5) to 3.3615(6) Å and from 2.961(1) to 3.380(1) Å for 1 and 2, respectively. A polymeric ribbon is obtained when four ligands link a given cluster to two others. The chains of 1, held only by van der Waals forces, pack in a hexagonal manner. The two water molecules in 2 (Ag−OH₂ = 2.385(7) Å) are coordinated to silver atoms of the cluster. They are also strongly hydrogen bonded to the oxygen atoms of two pentafluoropropionate groups, one within the cluster (O···O = 2.741(1) Å), the other in an adjacent chain (O···O = 2.818(1) Å). The chains, thus H bonded to one another, generate a 2D coordination network.