Simultaneous presence of mono- and bi-cationic bipyridyls within a metal-organic supramolecular host: crystal structure, spectral and Hirshfeld surface analysis

A new supramolecular metal-organic complex, {[Fe(CN)(6)](3-)(H(2)bipy)(2+)(Hbipy)(+)center dot 3H(2)O} (where bipy ipywhere biolecular metal-organic complex, {[Fe(CN)ccepted: 30 October 2022rized by single crystal X-ray crystallographic study (SC-XRD), powder X-ray diffraction (PXRD) and other spectroscopic analysis. Structural analysis reveals that the complex crystallizes in monoclinic space group P2(1)/c and is a 3 D supramolecular complex. Cyanide-water hydrogen bonding interactions between {Fe(CN)(6)}(3-) and guest water molecules form a wave-like 2 D supramolecular layer structure parallel to the crystallographic ac-plane with the formation of rectangular cavities of dimension 10.6 x 9.8 angstrom. These 2 D layers are further connected by O3W-H2W3 center dot center dot center dot O1W hydrogen bonding interactions to form a 3 D supramolecular structure with the creation of 1 D supramolecular channels along the crystallographic a-axis. The bi-cationic (H(2)bipy)(2+) form two different N+-H center dot center dot center dot water hydrogen bonding interactions (N8(+)-H8 center dot center dot center dot O2W and N7(+)-H7 center dot center dot center dot O3W) with two different water molecules and reside within the rectangular cavities. Monocationic (Hbipy)(+) moieties form a 1 D supramolecular chain structure through repetitive N center dot center dot center dot H-N+ hydrogen bonding interactions and are present within the 1 D supramolecular channels. In addition, these two different types of bipy moieties are interconnected to each other through pi center dot center dot center dot pi interactions. Hirshfeld surface analysis and the corresponding 2 D fingerprint plots clearly identify the presence of different types of supramolecular interactions between the two differently charged bipyridyl moieties and the host framework, and N-H/H-N contacts, corresponding to the hydrogen bonding interactions, have a significant contribution to the total surface. Both the absorption and emission spectra of the complex have also been studied.

Automated summary

This study reports the synthesis and structural characterization of a new supramolecular metal-organic complex. The complex exhibits a complex three-dimensional supramolecular structure, including two-dimensional layers and one-dimensional channels, connected by hydrogen bonding and π-π interactions between different molecular moieties. The spectroscopic properties of the complex have also been studied.