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

Fe[CHN][N(CN)] () was synthesized from a reaction of stoichiometric amounts of NaN(CN) and FeCl·4HO in a methanol/pyridine solution. Single-crystal and powder diffraction show that crystallizes in the monoclinic space group 2/ (no. 12), different from Mn[CHN][N(CN)] (2/, no. 14) due to tilted pyridine rings, with = 7.453(7) Å, = 13.167(13) Å, = 8.522(6) Å, = 114.98(6)° and = 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 Fe compound with predominantly antiferromagnetic exchange interactions at lower temperatures.