Hydrogen-bonded supramolecular structures in copper(II) nitrobenzoates with N-methylnicotinamide: synthesis, supramolecular structure, Hirshfeld surface analysis, spectral and DFT study

IF 1.6 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Transition Metal Chemistry Pub Date : 2023-07-27 DOI:10.1007/s11243-023-00542-x

Milan Piroš, Zuzana Vasková, Milan Mazúr, Ján Moncoľ, Jozef Švorec

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Abstract

The synthesis of six new copper(II) nitrobenzoate complexes with N-methylnicotinamide, used as an auxiliary ligand for a supramolecular interaction study, is reported. Crystal structures of six novel compounds [Cu(2-NO₂bz)₂(mna)₂(H₂O)₂] (1), [Cu(2-NO₂bz)₂(mna)₂(H₂O)₂]∙2H₂O (2), [Cu(3-NO₂bz)₂(mna)₂(H₂O)₂] (3), [Cu(3,5-(NO₂)₂bz)₂(mna)₂(H₂O)₂]∙2H₂O (4), [Cu(4-NO₂bz)₂(mna)₂(H₂O)₂]∙2(4-NO₂bzH) (5) and [Cu(3,5-(NO₂)₂bz)₂(mna)(H₂O)₃] (6) (mna = N-methylnicotinamide, 2-NO₂bz = 2-nitrobenzoate, 3-NO₂bz = 3-nitrobenzoate, 4-NO₂bz = 4-nitrobenzoate, 3,5-(NO₂)₂bz = 3,5-dinitrobenzoate) were determined by X-ray analysis. Compounds 1–6 are mononuclear with a tetragonal-bipyramidal geometry around the Cu²⁺ ion. The molecules of the studied complexes are mostly linked by a combination of N–H…O and O–H…O hydrogen bonds between N-methylnicotinamide and water molecules into supramolecular hydrogen-bonded coordination chains and networks. Intermolecular interactions in the supramolecular structures were also studied using Hirshfeld surface analysis. In addition, the complexes 1–6 have been characterised by elemental analysis, IR, UV–Vis and EPR spectroscopy. Density functional theory calculations were performed in order to reproduce the EPR magnetic parameters. DFT calculations of the EPR parameters show a good agreement with the experimental results.

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硝基苯甲酸铜- n-甲基烟酰胺氢键超分子结构:合成、超分子结构、Hirshfeld表面分析、光谱和DFT研究

报道了六种新型硝基苯甲酸铜与n -甲基烟酰胺配合物的合成，并作为辅助配体进行了超分子相互作用的研究。用x射线分析测定了6个新化合物[Cu(2- no2bz)2(mna)2(H2O)2](1)、[Cu(2- no2bz)2(mna)2(H2O)2]∙2H2O(2)、[Cu(3- no2bz)2(mna)2(H2O)2]∙2H2O(4)、[Cu(3,5- no2bz)2(mna)2(H2O)2]∙2(4- no2bz)2(H2O)2](5)和[Cu(3,5-(no2bz)2bz)2(mna)(H2O)3] (6) (mna = n -甲基烟酰胺、2- no2bz = 2-硝基苯甲酸盐、3- no2bz = 3-硝基苯甲酸盐、4- no2bz = 4-硝基苯甲酸盐、3,5-(NO2)2bz = 3,5-(NO2)2bz = 3,5-二硝基苯甲酸盐)2bz = 3,5-(NO2)2bz = 3,5-二硝基苯甲酸盐)2bz = 3,5-二硝基苯甲酸盐)。化合物1-6是单核的，在Cu2+离子周围呈四边形双锥体几何结构。所研究的配合物分子主要是通过n-甲基烟酰胺和水分子之间的N-H…O和O - h…O氢键组合成超分子氢键配位链和网络。利用Hirshfeld表面分析法研究了超分子结构中的分子间相互作用。此外，配合物1 ~ 6通过元素分析、IR、UV-Vis和EPR光谱进行了表征。密度泛函理论计算再现了EPR的磁性参数。EPR参数的DFT计算结果与实验结果吻合较好。

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来源期刊

Transition Metal Chemistry 化学-无机化学与核化学

CiteScore

3.60

自引率

0.00%

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审稿时长

1.3 months

期刊介绍： Transition Metal Chemistry is an international journal designed to deal with all aspects of the subject embodied in the title: the preparation of transition metal-based molecular compounds of all kinds (including complexes of the Group 12 elements), their structural, physical, kinetic, catalytic and biological properties, their use in chemical synthesis as well as their application in the widest context, their role in naturally occurring systems etc. Manuscripts submitted to the journal should be of broad appeal to the readership and for this reason, papers which are confined to more specialised studies such as the measurement of solution phase equilibria or thermal decomposition studies, or papers which include extensive material on f-block elements, or papers dealing with non-molecular materials, will not normally be considered for publication. Work describing new ligands or coordination geometries must provide sufficient evidence for the confident assignment of structural formulae; this will usually take the form of one or more X-ray crystal structures.