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Hydrogen-bonded network and layered supramolecular structures assembled from ClO4- counterions with unprecedented monomeric [AgL2]+ and chain polymeric [AgL2] nn+ complex cations (L = thioamide or thiourea-like ligands)

Lookup NU author(s): Emeritus Professor Bill CleggORCiD


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The complexes [Ag(etu)2]ClO4 (1) and [{Ag(py2tH) 2}-(ClO4)(H2O)0.5]n (2) have been obtained from the reactions of AgClO4 with the corresponding thioamide ligands (etu = imidazolidine-2-thione; py2tH = pyridine-2-thione). Complex 1, consisting of centrosymmetric monomeric [Ag(etu)2]+ cations and ClO4- counterions, constitutes the first bis[thio-(mono- or di)amide] complex (M = Cu, Ag) known thus far to possess a linear MS2 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 ClO4- 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]nn+ polymeric cations consisting of linear chains of linked Ag2(μ-S)2 rings, with distorted tetrahedral AgS4 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 H2O molecules and only one or two oxygen atoms of each ClO4- 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 M2(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.

Publication metadata

Author(s): Sola J, Lopez A, Coxall RA, Clegg W

Publication type: Article

Publication status: Published

Journal: European Journal of Inorganic Chemistry

Year: 2004

Issue: 24

Pages: 4871-4881

ISSN (print): 1434-1948

ISSN (electronic): 1099-0682

Publisher: Wiley - V C H Verlag GmbH & Co. KGaA


DOI: 10.1002/ejic.200300739


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