Versatile reaction of the potential host system [(Me3Sn) 4Ru(CN) 6]∞ with 4-thiopyridone/4-mercaptopyridine in water

Single crystals of three derivatives of the structurally still incompletely characterized coordination polymer [(Me₃Sn)₄Ru(CN)₆] 1b have been prepared and subjected to crystallographic studies: [1b · 4H₂O]=2b forms stacks of puckered _∞²[Ru{μ-CNSn(Me₃)NC}₂] sheets interlinked by hydrogen bonds in making use of two additional CNSn(Me₃)OH₂ ligands and quasi-zeolitic water. Mild drying of 2b leads to the “missing link” between 1b and 2b, [1b · 2H₂O], 3b. The structure of [1b · 2tp] (tp=4-thiopyridone) consists of a three-dimensional, negatively charged host framework comprising (via Sn-S bonds) one “aromatic” thione linkage and a [Me₃Sn · tp]⁺guest ion involving a more zwitterionic form of tp. Slow uptake of Me₃SnCl from the gas phase by an aqueous solution of K₄[Ru(CN)₆] and tp afforded the novel assembly [1b · 2H₂O · 0.8pms · 0.2pds] (pms/pds=4,4^′-dipyridylmono-/disulfide), the supramolecular architecture of which resembles that of 2b. Bridging pms or pds molecules occupy equivalent interlayer sites, and the pms/pds ratio is likely to vary. At least three further assemblies containing again 1b and either tp or pds/pms have likewise been isolated, however, not as single crystals.