New polymeric thiocyanatoiron(II) complex with N,N′-diethylnicotinamide – Synthesis, structure, magnetic and spectral properties

The iron(II) compound of formula [Fe(NCS)2(dena)2]n (dena = N,N  ′-diethylnicotinamide) has been prepared by the reaction between iron(III) thiocyanate and dena in ethanol solution. The complex was characterized by elemental analysis, spectral and magnetic measurements. Single-crystal X-ray diffraction methods show that the complex, crystallizing in the triclinic P1¯ space group, undergoes a phase transition between 220 K and 230 K, connected with the doubling of cell volume. Crystal structures at 230 K (1a; HT phase) and 150 K (1b; LT phase) are described and a transition mechanism is discussed. In both phases the compound has an extended chain structure, in which the neutral molecule of N,N′-diethylnicotinamide acts as a bridging ligand binding through pyridine N atom to one centre and through amide O atom to the neighbouring Fe centre. The Fe2+ ion has a slightly distorted trans-octahedral environment with FeO2N4 chromophore, and all Fe–O and Fe–N bonds in the typical for high-spin iron(II) compounds range. Variable-temperature magnetic susceptibility data in the temperature range 1.8–300 K show that iron(II) is high-spin S = 2(5T2g) and as a result effects due to zero-field splitting are anticipated at low temperatures. The IR spectrum suggested the coordination of N,N′-diethylnicotinamide to the central atom of iron(II) as a bridging ligand and NCS group as a monodentate ligand.

The synthesis, crystal structure, spectral and magnetic properties are reported for the new compound of formula [Fe(NCS)2(dena)2]n (dena = N,N′-diethylnicotinamide). The complex crystallizes in the triclinic space group and undergoes a phase transition between 220 K and 230 K, connected with the doubling of a cell volume. In both phases the compound has an extended chain structure, in which the neutral molecule of N,N′-diethylnicotinamide acts as a bridging ligand binding through pyridine N atom to one centre and through amide O atom to the neighbouring Fe centre. The Fe2+ ion has a slightly distorted trans-octahedral environment with FeO2N4 chromophore and all Fe–O and Fe–N bonds in the typical for high-spin iron(II) compounds range. This magnetic data show that the iron(II) is high-spin S = 2(5T2g) and as a result effects due to zero-field splitting are anticipated at low temperatures. The IR spectrum suggested coordination of N,N′-diethylnicotinamide to the central atom of iron(II) as a bridging ligand and NCS group as a monodentate ligand.Figure optionsDownload as PowerPoint slide