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–).