| A surge of research activity in the development of specific structure architectures involve the self-assembly of molecules or ions into well-defined supra-molecules via intermolecular interactions such as hydrogen bonding and Ï€-Ï€ stacking. These intermolecular interactions play an important effect on the organizations and properties of many materials and biological systems such as PSI, PSII, water channels, ion channels and so on.We expect to understand the supra-molecular structures assembled by hydrogen bonding and Ï€-Ï€ stacking, and investigate the nature of intermolecular interactions by studies on crystal structures of metallic complexes and their supra-molecular structure assembled by intermolecular interactions.In this work 11 new metallic complexes were synthesized, in which o-hydroxybenzoate (oHBA), m-hydroxybenzoate (mHBA) or p-hydroxybenzoate (pHBA) acts as anion ligands, and benzimidazole (bzim), 1,10-phenanthlorine (phen) or 2,2'-bipyridine (bipy) as neutral ligands. Their three-dimesional structures were determined by single X-ray diffraction method. The 11 complexes are as follows:(â… ), [Cu2(bzim)4(mHBA)4][Cu(bzim)2(mHBA)2]·6H2O;(â…¡), [Cu(bzim)2(pHBA)2];(â…¢), [Cu(phen)(pHBA)2];(â…£), [Co(phen)2(mHBA)(H2O)](mHBA)·4.5H2O;(â…¤), [Co(phen)(pHBA)2(H2O)2]·H2O;(â…¥), [Mn(phen)(oHBA)2]n;(â…¦),[Mn(phen)2(mHBA)(H2O)](mHBA);(â…§), [Mn(phen)2(pHBA)(H2O)](pHBA)·H2O;(â…¨), [Sr(phen)2(oHBA)2(H2O)2];(â…©), [Ni(phen)2Cl(H2O)]Cl·(pHBAH)H2O;(â…ª), [Mn(bipy)2pHBA)2].Several following conclusions are obtained through studies on crystal structures of these complexes.1. A new criterion to decide whether the carboxy group coordinating to the metallic ion in mono or bi dentate-fashion in an ambiguous situation, base on coordination bond distances and angles.2. Large Metal-Ocarboxy-C coordination bond angles with normal corresponding coordination bond distances imply the Metal-Ocarboxy coordination bonds contain genuine electrostatic interactions.3. The charge of metallic ions affects the formation of aromatic Ï€-Ï€ stacking interaction between metal-coordinated, nonpolar aromatic rings (e.g. benzene rings). The more positive the charge of metallic ions is, the more favorably the Ï€-Ï€ stacking interactions form between the metal-coordinated, nonpolar aromatic rings.4. The aromatic Ï€-Ï€ stacking interactions strongly affect the configuration of complexes and their molecular packing, studied on multi-dimensional supra-molecular structures assembled by aromatic Ï€-Ï€ stacking and hydrogen-bonding interactions. |
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