Hydrogen‐Bonded Network and Layered Supramolecular Structures Assembled from ClO 4 − Counterions with Unprecedented Monomeric [AgL 2 ] + and Chain Polymeric [AgL 2 ] n n+ Complex Cations (L = Thioamide or Thiourea‐Like Ligands)

The complexes [Ag(etu) 2 ]ClO 4 ( 1 ) and [{Ag(py2tH) 2 }(ClO 4 )(H 2 O) 0.5 ] n ( 2 ) have been obtained from the reactions of AgClO 4 with the corresponding thioamide ligands (etu = imidazolidine‐2‐thione; py2tH = pyridine‐2‐thione). Complex 1 , consisting of centrosymmetric monomeric [Ag(etu) 2 ] + cations and ClO 4 − counterions, constitutes the first bis[thio(mono‐ or di)amide] complex (M = Cu, Ag) known thus far to possess a linear MS 2 mononuclear core. Component ions behave in the crystal structure as complementary partners, with all four N−H groups of each [Ag(etu) 2 ] + cation and all four oxygen atoms of each ClO 4 − anion involved in N−H···O−Cl hydrogen bonding associations. This leads to the assembly of a three‐dimensional supramolecular network. Complex 2 , whose previously reported structure has been redetermined with higher precision, contains catena‐ [Ag(py2tH) 2 ] n n + polymeric cations consisting of linear chains of linked Ag 2 (μ‐S) 2 rings, with distorted tetrahedral AgS 4 centres. Supramolecular association through N−H···O−Cl, N−H···O(water) and Cl−O···H−O−H···O−Cl hydrogen bonding, where all N−H groups and H 2 O molecules and only one or two oxygen atoms of each ClO 4 − anion are involved, leads to the formation of a two‐dimensional layered supramolecular structure. A correlation of some stereochemical parameters and a simple qualitative sulfur‐bridge bonding model has been developed for 2 and other related thioamide complexes containing M 2 (μ‐S) 2 rings or M−S−M′ single bridges. For these structural units, suitable ranges of tilt and twist dihedral angles have been estimated and assigned to different bonding types. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)