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

Two topologically comparable complexes, [Ag6(CF3CO2)3(L1-Me)3(SCH3)3]∞ (1) and [Ag6(CF3CF2CO2)3(L1-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, L1-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.