Synthesis and Characterization of Iron Bispyridine Bisdicyanamide, Fe[C5H5N]2[N(CN)2]2.

Fe[C5H5N]2[N(CN)2]2 (1) was synthesized from a reaction of stoichiometric amounts of NaN(CN)2 and FeCl2·4H2O in a methanol/pyridine solution. Single-crystal and powder diffraction show that 1 crystallizes in the monoclinic space group I2/m (no. 12), different from Mn[C5H5N]2[N(CN)2]2 (P21/c, no. 14) due to tilted pyridine rings, with a = 7.453(7) Å, b = 13.167(13) Å, c = 8.522(6) Å, ß = 114.98(6)° and Z = 2. ATR-IR, AAS, and CHN measurements confirm the presence of dicyanamide and pyridine. Thermogravimetric analysis shows that π-stacking interactions of the pyridine rings play an important role in structural stabilization. Based on DFT-optimized structures, a chemical bonding analysis was performed using a local-orbital framework by projection from a plane-wave basis. The resulting bond orders and atomic charges are in good agreement with the expectations based on the structure analysis. SQUID magnetic susceptibility measurements show a high-spin state FeII compound with predominantly antiferromagnetic exchange interactions at lower temperatures.

Nickel hexa-yttrium deca-iodide, [NiY6]I10.

Comproportionation reactions of yttrium triiodide, yttrium and nickel led to the formation of the compound [NiY6]I10, which is isostructural with the prototypical [RuY6]I10. In particular, [NiY6]I10 is composed of isolated nickel centered yttrium octa-hedra (site symmetry -1) that are further surrounded by iodide ligands to construct a three-dimensional cluster complex framework. Although this compound has been previously detected by powder X-ray diffraction techniques [Payne & Corbett (1990 ▶). Inorg. Chem. 29, 2246-2251], details of the crystal structure for triclinic [NiY6]I10 were not provided.