Abstract
The present work assesses the ability of two flexible bis-tetrazole organosulfur ligands to build up different metallosupramolecular compounds based on the analysis of the different supramolecular interactions. The reaction of copper(II) chloride dihydrate with the N,N’-donor dithioether ligands bis(1-methyl-1H-tetrazole-5-ylthio)methane (BMTTM) and 1,2-bis(1-methyl-1H-tetrazole-5-ylthio)ethane (BMTTE) was investigated using different synthetic methods. Four compounds have been obtained as single crystals: two pseudopolymorphic 1D Cu(II) coordination polymers with the ligand BMTTM, a 2D Cu(II) coordination polymer and a discrete Cu(I) tetramer with the BMTTE ligand. The effects of the weak interactions on the crystal packing and the Hirshfeld surfaces of the structures were analyzed to clarify the nature of the intermolecular interactions.
Highlights
Well-defined supramolecular architectures produced by the formation of ordered crystalline materials have attracted considerable attention in recent years due to their different novel chemical properties and their possible new applications
Supramolecular metal–organic frameworks (SMOFs) are materials that can be considered as analogs to metal–organic frameworks (MOFs) in the sense that some coordination bonds are replaced by hydrogen bonds as directional interactions to build the final crystal
In supramolecular metal–organic frameworks (SMOFs), the coordination bonds are released from guiding the crystal structure and supramolecular interactions play this role instead
Summary
Well-defined supramolecular architectures produced by the formation of ordered crystalline materials have attracted considerable attention in recent years due to their different novel chemical properties and their possible new applications. In the field of metallosupramolecular chemistry, these compounds are interesting since the tetrazole moiety contains several nitrogen atoms that can facilitate simultaneously the coordination to one or more metal centers and the formation of hydrogen bonds acting as acceptors. With the aim of studying the role of C–H· · · X (X = Cl, S, N) hydrogen bonds in the crystalline supramolecular networks based on copper(II/I) chloride/bis-tetrazole organosulfur systems, we report here the crystal structures of four compounds resulting from reactions under different synthetic conditions between the ligands bis(1-methyl-1H-tetrazole-5-ylthio)methane (BMTTM) and. These ligands have attractive features, such as the multiple heteroatomic potential coordination sites, six N donors and two S atoms, which contribute to the flexibility of the ligands. A study of the weak interactions responsible for the supramolecular organization has not been undertaken for any of these compounds
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