Much attention has been lately devoted to the construction of different crystal architectures. Although several approaches have been tried these involving hydrogen bonds were found especially useful. For metal complexes, however, N-H^…S interactions known for their very important role in biological systems, did not find a widespread use. The structures of ammonium silanethiolates were reported with the charge assisted N-H···S hydrogen bond as a structure forming factor [1]. Now, we have obtained manganese(II) trialkoxysilanethiolate complexes incorporating aminopyridines as coligands and found that their structures reflect the ability of the neutral silanethiolate sulfur atom to serve as the N-H···S bond acceptor as well [2]. Pursuing further our studies we have synthesized a series of new silanethiolate complexes of cadmium(II). In all syntheses [Cd{SSi(OBu^t)₃}₂]₂ [3] served as a substrate and 2-, 3- and 4-aminopyridines were chosen as additional ligands. For comparison 4-dimethylaminopyridine was also used. For all colorless crystalline products molecular structure has been determined. Again, the formation of N­­-H···S hydrogen bonds was observed and their significant influence on the structure of the complexes established. Two complexes may serve as examples. In the case of 2-aminopyridine a complex containing only one molecule of the N-donor ligand was formed [Cd{SSi(OBu^t)₃}₂(2-NH₂py)] and the amino group has been found to act as a donor of the intramolecular N-H…S bond to one of the thiolate sulfur atoms. The same R(6) motif was found previously in the related manganese(II) containing complex. When less sterically hindered 3-aminopyridine was used not only two N-donor ligands entered the cadmium coordination sphere (compared to only one in the Mn-containing complex) but also bimetallic complex [Cd{SSi(OBu^t)₃}₂(3-NH₂py)₂]₂ was formed. Its molecular structure, showing the role of intermolecular N-H···S hydrogen bonds is shown in the picture.

[1] B. Becker, K. Baranowska, J. Chojnacki, W. Wojnowski, Chem. Comm. 2004, 620.

[2] A. Kropidłowska, J. Chojnacki, B. Becker, 48 Zjazd PTChem i SITPChem, Poznań, 2005, Abstracts, S3-K7.

[3] W. Wojnowski, B. Becker, L. Walz, K. Peters, E.-M. Peters, H. G. von Schnering, Polyhedron 1992, 11, 607.

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