Abstract
The supramolecular structures of the three metal (II) azido complexes [Fe(4bzpy)4(N3)2]; 1, [Ni(4bzpy)4(N3)2]; 2 and [Zn(4bzpy)2(N3)2]n; 3 with 4-benzoylpyridine (4bzpy) were presented. All complexes contain hexa-coordinated divalent metal ions with a slightly distorted octahedral MN6 coordination sphere. Complexes 1 and 2 are monomeric with terminal azido groups while 3 is one-dimensional coordination polymer containing azido groups with μ(1,1) and μ(1,3) bridging modes of bonding. Hirshfeld analysis was used to quantitatively determine the different contacts affecting the molecular packing in the studied complexes. The most common interactions are the polar O…H and N…H interactions and the hydrophobic C…H contacts. The charges at the M(II) sites are calculated to be 1.004, 0.847, and 1.147 e for complexes 1–3, respectively. The degree of asymmetry is the highest in the case of the terminal azide in complexes 1 and 2 while was found the lowest in the μ(1,1) and μ(1,3) azide bonding modes in the Zn(II) complex 3. These facts were further explained in terms of atoms in molecules (AIM) topological parameters.
Highlights
In supramolecular solid-state chemistry of metal-organic complexes, the framework constructions are based on the arrangement of the molecular building blocks by strong hydrogen bonds or dative coordination bonds
An important class of supramolecular chemistry known as metallosupramolecular chemistry which is based upon the self-assembly of metal ions and organic ligands [1,2]
Metallosupramolecular chemistry has an important contribution to the spectacular development of crystal engineering [3,4,5,6,7,8,9,10]
Summary
In supramolecular solid-state chemistry of metal-organic complexes, the framework constructions are based on the arrangement of the molecular building blocks by strong hydrogen bonds or dative coordination bonds. An important class of supramolecular chemistry known as metallosupramolecular chemistry which is based upon the self-assembly of metal ions and organic ligands [1,2]. Self-assembly is one of the most appropriate synthetic routes to build metallosupramolecular structures with interesting multidimensional and topological structures [11,12,13,14,15,16,17,18,19,20] These can be achieved by proper selection of the suitable metal ion, ligand, and co-ligand [21,22]. The importance of the coordinated azides is due to the capability of the azide group to have different modes of bonding as it acts as a terminal ligand (mono-dentate) or bridging ligand with several. Found: C, 55.61; H, 3.43; N, 21.66; Zn, 12.54%
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