The quality of single crystals of 39 was not good enough to diffract well, which prevented the exact determination of its structure even at 173 K. But its actual network can be observed by seeing 173 K data, which was isostructural to 38. Single Crystal structure of 38 at 100 K showed that it crystallized in the orthorhombic space group of Pmmm. It consisted of [Fe(L19)Ag(CN)2] + polymeric ion, in which the Fe(II) centers were bridged by L19 and [Ag(CN)2] -anion to build the 3D cationic CP (Fig. ). The ClO4 -counteranions and various solvent molecules were present within the cavity of the network. Fe(II) centers were attached with four N atoms from L19 ligands situated in the equatorial plane, two N atoms of [Ag(CN)2] -bridging ligands positioned at the axial positions. At 260 K, the unit cell volume was higher than four times as compared to that of at 100 K and the space group of the crystal system became Cmmm.