Fe[C5H5N]2[N(CN)2]2(1) was synthesized from a reaction of stoichiometric amounts of NaN(CN)2and FeCl2·4H2O in a methanol/pyridine solution. Single-crystal and powder diffraction show that1crystallizes in the monoclinic space groupI2/m(no. 12), different from Mn[C5H5N]2[N(CN)2]2(P21/c, no. 14) due to tilted pyridine rings, witha= 7.453(7) Å,b= 13.167(13) Å,c= 8.522(6) Å,β= 114.98(6)° andZ= 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 FeIIcompound with predominantly antiferromagnetic exchange interactions at lower temperatures.