Synthesis and structure of Zn(II) and Cu(II) complexes derived from 2-(aminomethyl)benzimidazole and glycine

Name: Synthesis and structure of Zn(II) and Cu(II) complexes derived from 2-(aminomethyl)benzimidazole and glycine
Creator: Taylor & Francis
Published: 2020-09-04 22:52:42
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DataCite Commons2020-09-04 更新2024-07-25 收录

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Reactions of 2-(aminomethyl)benzimidazole di-hydrochloride (1·2HCl) and glycine with 3Zn(OH)2·2ZnCO3 or Cu(OAc)2·H2O led to the synthesis of the quaternary coordination complexes 2 and 3. X-ray diffraction showed that these complexes are composed of 2a = [Zn(L)Cl(L′)] and 2b = [Zn(L)(H2O)2(L′)], and of 3a = [Cu(L)(H2O)0.25Cl(L′)] and 3b = [Cu(L)(H2O)1.5(L′)], respectively, where L = 2-(aminomethyl)benzimidazole and L′ = glycinate. Zn(II) in 2a has an intermediate geometry between a square-pyramid and a trigonal bipyramid structure. However, the geometry about the metal ion of units 2b, 3a, and 3b is distorted octahedral. Moreover, the supramolecular structures for 2 and 3 were assembled through N–H⋯O and O–H⋯Cl hydrogen bonds. In these complexes, H2O and N–H groups serve as proton donors, whereas chloride and C=O groups serve as proton acceptors. Also π–π stacking interactions between aromatic rings contribute to the stabilization of the supramolecular structure of 2 and 3. The Zn and Cu complexes were studied by infrared and Raman spectroscopy, which indicated that 2 and 3 have similar molecular structures in the solid state. Ultrasound activation at the end of the reaction was necessary to yield 2.

以二盐酸盐2-(氨甲基)苯并咪唑（2-(aminomethyl)benzimidazole di-hydrochloride，记为1·2HCl）与甘氨酸为反应物，分别与碱式碳酸锌（3Zn(OH)₂·2ZnCO₃）和一水合乙酸铜（Cu(OAc)₂·H₂O）进行反应，成功合成了四元配位配合物2与3。X射线衍射（X-ray diffraction）分析显示，配合物2与3分别由两种结构单元构成：2a = [Zn(L)Cl(L′)]、2b = [Zn(L)(H₂O)₂(L′)]以及3a = [Cu(L)(H₂O)₀.₂₅Cl(L′)]、3b = [Cu(L)(H₂O)₁.₅(L′)]，其中L代表2-(氨甲基)苯并咪唑，L′代表甘氨酸根。2a中的Zn(II)中心离子的配位几何构型介于四方锥与三角双锥之间；而2b、3a与3b的金属中心配位几何均为畸变八面体构型。此外，配合物2与3的超分子结构通过N–H⋯O与O–H⋯Cl氢键组装得到：在此类配合物中，H₂O与N–H基团作为质子给体，氯离子与C=O基团则作为质子受体。同时，芳香环间的π–π堆积（π–π stacking）相互作用也有助于稳定2与3的超分子结构。采用红外光谱与拉曼光谱对上述锌、铜配合物进行表征，结果表明2与3在固态下具有相似的分子结构。反应末期需进行超声活化处理，方可合成配合物2。

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Taylor & Francis

创建时间：

2016-01-19