Hamamci Alisir Sevim, Dege Necmi, Tapramaz Recep
Ondokuz Mayis University, Faculty of Engineering, Department of Metallurgical & Materials Engineering, Samsun 55139, Turkey.
Ondokuz Mayis University, Faculty of Arts and Sciences, Department of Physics, Samsun 55139, Turkey.
Acta Crystallogr C Struct Chem. 2019 Apr 1;75(Pt 4):388-397. doi: 10.1107/S2053229619001827. Epub 2019 Mar 4.
Three new diclofenac-based copper(II) complexes, namely tetrakis{μ-2-[2-(2,6-dichloroanilino)phenyl]acetato-κO:O'}bis(methanol-κO)copper(II), [Cu(μ-dicl)(CHOH)] (1), bis{2-[2-(2,6-dichloroanilino)phenyl]acetato-κO,O'}bis(1-vinyl-1H-imidazole-κN)copper(II), [Cu(dicl)(vim)] (2), and bis{2-[2-(2,6-dichloroanilino)phenyl]acetato-κO,O'}bis(1H-imidazole-κN)copper(II), [Cu(dicl)(im)] (3) [dicl is diclofenac (CHClNO), vim is 1-vinylimidazole (CHN) and im is imidazole (CHN)], have been synthesized and characterized by elemental analysis, FT-IR spectroscopy, thermal analysis and single-crystal X-ray diffraction. X-ray diffraction analysis shows that complex 1 consists of dimeric units in which the dicl ligand exhibits a bidentate syn,syn-μ coordination mode linking two copper(II) centres. Complexes 2 and 3 have mononuclear units with the general formula [Cu(dicl)L] (L is vim or im) in which the Cu ions are octahedrally coordinated by two L and two dicl chelating ligands. The L and dicl ligands both occupy the trans positions of the coordination octahedron. The different coordination modes of dicl in the title complexes were revealed by Fourier transform IR (FT-IR) spectroscopy. The spin matching between the copper(II) centres in the dimeric [Cu(μ-dicl)(CHOH)] units was also confirmed by magnetic data to be lower than the spin-only value and electron paramagnetic resonance (EPR) spectra. The thermal properties of the complexes were investigated by thermogravimetric (TG) and differential thermal analysis (DTA) techniques.
合成了三种基于双氯芬酸的铜（II）配合物，即四{μ-2-[2-(2,6-二氯苯胺基)苯基]乙酸根-κO:O'}双（甲醇-κO）铜（II），[Cu(μ-dicl)(CH₃OH)]₂ (1)、双{2-[2-(2,6-二氯苯胺基)苯基]乙酸根-κO,O'}双（1-乙烯基-1H-咪唑-κN）铜（II），[Cu(dicl)(vim)] (2)和双{2-[2-(2,6-二氯苯胺基)苯基]乙酸根-κO,O'}双（1H-咪唑-κN）铜（II），[Cu(dicl)(im)] (3) [dicl为双氯芬酸（C₁₄H₁₀Cl₂NO₂），vim为1-乙烯基咪唑（C₅H₆N₂），im为咪唑（C₃H₄N₂）]，并通过元素分析、傅里叶变换红外光谱（FT-IR）、热分析和单晶X射线衍射对其进行了表征。X射线衍射分析表明，配合物1由二聚体单元组成，其中双氯芬酸配体呈现双齿顺式、顺式-μ配位模式，连接两个铜（II）中心。配合物2和3具有通式为[Cu(dicl)L]（L为vim或im）的单核单元，其中铜离子由两个L和两个双氯芬酸螯合配体八面体配位。L和双氯芬酸配体均占据配位八面体的反位。通过傅里叶变换红外（FT-IR）光谱揭示了标题配合物中双氯芬酸的不同配位模式。二聚体[Cu(μ-dicl)(CH₃OH)]₂单元中铜（II）中心之间的自旋匹配也通过磁数据得到证实，低于仅自旋值和电子顺磁共振（EPR）光谱。通过热重（TG）和差示热分析（DTA）技术研究了配合物的热性质。
