Structural Study of Alkaline 1‐Phenyl‐1H‐1, 2, 3, 4‐tetrazole‐5‐thiolate Salts: An Example of Periodicity in Alkaline Cations

The alkaline 1‐phenyl‐1H‐1, 2, 3, 4‐tetrazole‐5‐thiolate salts, M[C6H5N4CS] (M = Li (1), Na (2), K (3), Rb (4) and Cs (5)) were obtained and characterized by means of mass spectrometry (FAB+) and NMR (1H; 13C) spectroscopy. The structures of Na (2), K (3), Rb (4) and Cs (5) compounds were determined by X‐ray diffraction methods. The ligand shows a rich variety of coordination patterns with the alkaline cations. The formation of a four‐membered ring MSCN in the compounds with heavier alkali cations (K, Rb and Cs) is shown. In all the cations the coordination number around it increases with the ionic radius. Compounds with Cs+ and Rb+ exhibited the formation of Cs‐C and Rb‐C interactions with the phenyl group.