Cadmium complexes of thiones. Part II.1 A synthetic, solution, and solid-state MAS 111/113Cd NMR study of cadmium complexes of 1,3-thiazolidine-2-thione, and the structures of [tetrakis(1,3-thiazolidine-2-thione)cadmium] trifluoromethanesulfonate ([Cd(C3H5NS2)4](CF3SO3)2) and [tetrakis(1,3-thiazolidine-2-thione)cadmium][tetrakis(nitrato-O,O')cadmate] ([Cd(C3H5NS2)4][Cd(O2NO)4

Abstract

Treatment of Cd(O3SCF3)2 with the stoichiometric quantity of 1,3-thiazolidine-2-thione (tztH) allows isolation of [Cd(tztH)4](O3SCF3)2 (1). When tztH:Cd [Formula: see text] 2 the reaction of Cd(NO3)2·4H2O with tztH leads to [Cd(tztH)4][Cd(O2NO)4] (2). The structures of both 1 and 2 have been determined by single crystal X-ray analysis. Colourless crystals of 1 are orthorhombic, space group Fdd2, with eight molecules per unit cell (Z = 8) of dimensions a = 20.139(3), b = 23.332(5), c = 14.214(3) Å. Those of 2 are tetragonal, space group I [Formula: see text], with four molecules per unit cell (Z = 4) of dimensions a = 13.8853(11), c = 8.077(2) Å. The discrete homoleptic cation [Cd(tztH)4]2+ is characterized for the first time in 1 and 2. The cations are of point group symmetry C2 and S4 in 1 and 2, respectively. In both cases the ligands are S-bound, and the CdS4 kernel is a squashed tetrahedron. In 2, the eight-coordinate anion [Cd(O2NO)4]2- is characterized for the second time. 113Cd CP MAS NMR data are reported for solid 1 and 2, and also for solids produced by fusing Cd(NO3)2·4H2O with different molar ratios amounts of tztH, and by fusing Cd(O3SCF3)2 with six mol equivalents of tztH. In the Cd(NO3)2·4H2O:tztH mixtures, species identified include unreacted cadmium salt 2 ([Cd(tztH)4](NO3)2) and possibly Cd(tztH)3(NO3)2. [Cd(tztH)4](NO3)2 becomes the major species only when a significant excess of tztH is used. In the mixtures with tztH:Cd > 4, neither Cd(NO3)2·4H2O nor Cd(O3SCF3)2 form complexes containing more than four tztH ligands. Reduced-temperature 111Cd NMR data are reported for Cd(ClO4)2·6H2O:tztH mixtures in MeOH. Species identified are Cd(tztH)w2+(solv) (w = 0–3).Key words: 1,3-thiazolidine-2-thione, cadmium complexes, X-ray analysis, 113Cd CP MAS NMR, solution 111Cd NMR, tetrakis(1,3-thiazolidine-2-thione)cadmium(2+) cation, tetrakis(nitrato-O,O')cadmate(2–) anion.