A nitrogen-rich ligand bis(1H-tetrazol-5-yl)amine (H(3)bta) was employed to isolate a new Fe-III complex, Na2NH4[Fe-III(Hbta)(3)]center dot 3DMF center dot 2H(2)O (1). Single crystal X-ray diffraction revealed that complex 1 consists of Fe-III ions in an octahedral environment where each metal ion is coordinated by three Hbta(2-) ligands forming the [Fe-III(Hbta)(3)](3-) core. Each unit is linked to two one-dimensional (1-D) Na+/solvent chains creating a two-dimensional (2-D) network. In addition, the presence of multiple hydrogen bonds in all directions between ammonium cation and ligands of different [Fe-III(Hbta)(3)](3-) units generates a three-dimensional (3-D) network. Magnetic measurements confirmed that the Fe-III center undergoes a Spin Crossover (SCO) at high temperature (T-1/2 = 460(10) K).