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首页> 外文期刊>Acta crystallographica. Section C, Structural chemistry. >Four supramolecular isomers of dichloridobis(1,10-phenanthroline)cobalt(II): synthesis, structure characterization and isomerization
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Four supramolecular isomers of dichloridobis(1,10-phenanthroline)cobalt(II): synthesis, structure characterization and isomerization

机译：二氯双（1,10-菲咯啉）钴（II）的四种超分子异构体：合成，结构表征和异构化

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Crystal engineering can be described as the understanding of intermolecular interactions in the context of crystal packing and the utilization of such understanding to design new solids with desired physical and chemical properties. Free-energy differences between supramolecular isomers are generally small and minor changes in the crystallization conditions may result in the occurrence of new isomers. The study of supramolecular isomerism will help us to understand the mechanism of crystallization, a very central concept of crystal engineering. Two supramolecular isomers of dichloridobis(1,10-phenanthroline-κ2N,N′)cobalt(II), [CoCl2(C12H8N2)2], i.e. (IA) (orthorhombic) and (IB) (monoclinic), and two supramolecular isomers of dichloridobis(1,10-phenanthroline-κ2N,N′)cobalt(II) N,N-dimethylformamide monosolvate, [CoCl2(C12H8N2)2]·C3H7NO, i.e. (IIA) (orthorhombic) and (IIB) (monoclinic), were synthesized in dimethylformamide (DMF) and structurally characterized. Of these, (IA) and (IIA) have been prepared and structurally characterized previously [Li et al. (2007). Acta Cryst. E63, m1880–m1880; Cai et al. (2008). Acta Cryst. E64, m1328–m1329]. We found that the heating rate is a key factor for the crystallization of (IA) or (IB), while the temperature difference is responsible for the crystallization of (IIA) or (IIB). Based on the crystallization conditions, isomerization behaviour, the KPI (Kitajgorodskij packing index) values and the density data, (IB) and (IIA) are assigned as the thermodynamic and stable kinetic isomers, respectively, while (IA) and (IIB) are assigned as the metastable kinetic products. The 1,10-phenanthroline (phen) ligands interact with each other through offset face-to-face (OFF) π–π stacking in (IB) and (IIB), but by edge-to-face (EF) C—H...π interactions in (IA) and (IIA). Meanwhile, the DMF molecules in (IIB) connect to neighbouring [CoCl2(phen)2] units through two C—H...Cl hydrogen bonds, whereas there are no obvious interactions between DMF molecules and [CoCl2(phen)2] units in (IIA). Since OFF π–π stacking is generally stronger than EF C—H...π interactions for transition-metal complexes with nitrogen-containing aromatic ligands, (IIA) is among the uncommon examples that are stable and densely packed but that do not following Etter's intermolecular interaction hierarchy.
机译：可以将晶体工程描述为对晶体堆积背景下分子间相互作用的理解，以及利用这种理解来设计具有所需物理和化学性质的新固体。超分子异构体之间的自由能差异通常很小，并且结晶条件的细微变化可能导致新异构体的出现。超分子异构现象的研究将帮助我们理解结晶的机制，这是晶体工程的一个非常重要的概念。二氯双（1,10-菲咯啉-κ2N，N'）钴（II）[CoCl2（C12H8N2）2]（即（IA）（斜方）和（IB）（单斜））的两个超分子异构体，以及二氯双（1,10-菲咯啉-κ2N，N'）钴（II）N，N-二甲基甲酰胺单溶剂化物，[CoCl2（C12H8N2）2]·C3H7NO，即（IIA）（斜方）和（IIB）（单斜）在二甲基甲酰胺（DMF）中合成并进行结构表征。其中，（IA）和（IIA）已被制备并在结构上进行了表征[Li等人，J.Biol.Chem。，2004，6，1897]。 （2007）。 Acta Cryst。 E63，m1880–m1880;蔡等。 （2008）。 Acta Cryst。 E64，m1328–m1329]。我们发现加热速率是（IA）或（IB）结晶的关键因素，而温差则是（IIA）或（IIB）结晶的原因。根据结晶条件，异构化行为，KPI（Kitajgorodskij堆积指数）值和密度数据（IB）和（IIA）分别指定为热力学和稳定动力学异构体，而（IA）和（IIB）分别为被指定为亚稳态动力学产物。 1,10-菲咯啉（phen）配体通过在（IB）和（IIB）中错开的面对面（OFF）π-π堆叠而相互相互作用，但通过边对面（EF）CH相互作用...在（IA）和（IIA）中的相互作用。同时，（IIB）中的DMF分子通过两个CH ... Cl氢键连接到相邻的[CoCl2（phen）2]单元，而DMF分子与[CoCl2（phen）2]单元之间没有明显的相互作用在（IIA）中。对于具有含氮芳香族配体的过渡金属络合物，由于OFF π–π堆积通常比EF C-H ...π相互作用更强，因此（IIA）是稳定且密集堆积但不遵循的罕见例子Etter的分子间相互作用层次结构。

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