Single-crystal X-ray diffraction of 1•2DMF•H2O was performed at 120 and 240 K where it crystallizes in a monoclinic space group C2/c forming a 3D hexagonal coordination network (Table ) connecting the molybdenum and iron centers via cyanide bridge. The asymmetric unit is made up of two crystallographically independent Fe(II) centers on a glide plane and one Mo(V) center on a 2-fold axis, with each contributing half to the unit cell along with one BF4 - counter anion and two DMF and one water molecule. The coordination geometry of [Mo V (CN)8] 3-ion is best described as a distorted square antiprism (continuous shape measures (CShM) program, Table -S9) with MoC8 surrounding from four terminal and four carbon donor atoms from four bridging cyanide ligands. The Fe(II) ions are six-coordinate and adopt pseudo-octahedral geometry both in 120 and 240 K confirmed by CShM analysis (Table -S9). The coordination environment around Fe1 and Fe2 centers are satisfied with four imidazolyl nitrogen atoms coming from the vinyl imidazole ligand and two nitrogen atom of bridging cyanide group from [Mo(CN)8] 3-. Among the four bridging cyanides of [Mo(CN)8] 3-unit, two of them are bridged with two Fe2 centers along the ac direction and the other two cyanides are bridged to Fe1 along the b direction resulting a 3D hexagonal network (Figure & S4). This alternate cyanide-bridged Mo and Fe 3D network contains 12 membered {Mo6Fe6}n hexagonal rings. The water and DMF molecules occupy the pore inside the crystal structure which has a length of 24.880 Å and width of 14.568 Å. There are several H-bonding interactions present in the crystal structure between the solvent molecules (DMF and H2O) and nitrogen atoms of free cyanide from [Mo(CN)8] 3-unit (Figure , left).