FTIR spectroscopic and thermal study of M(Cyclohexanethiol)2Ni(CN)4·(1,4-dioxane) clathrate (M = Mn, Co, Ni and Cd)

In this study, clathrate of Cyclohexanethiol-tetracyanonickel-dioxane, given by the formula M(Cyclohexanethiol)2Ni(CN)4·(l,4-dioxane) (M = Mn, Co, Ni and Cd), is obtained for the first time through chemical methods. The FTIR spectroscopic data in the region of (4000-400) cm−1 was recorded and the IR frequencies were given and explained in detail. The thermal behavior of these clathrates was also investigated by thermo-gravimetric analysis (TGA), differential thermal analysis (DTA) and derivative thermal gravimetric analysis (DTG). The spectral and thermal analysis results of the newly synthesized clathrate of Cyclohexanethiol-tetracyanonickel-dioxane suggest that these clathrates are new examples of the Hofmann-type clathrates. In our study, the Hofmann-type clathrates formed by bounding electrons of sulfur-donor atoms of the thiol group of Cyclohexanethiol ligand molecule to transition metal atoms consist of the corrugated |M-Ni(CN)4|∞ polymeric layers which are held in parallel through the van der Walls interactions (-M-Cyclohexanethiol⋯Cyclohexanethiol-M-).