Ammonium 18-crown-6 complexes with tetrahedral monoanions: X-ray, thermal and comparative analysis of non-covalent interactions†

IF 2.6 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

CrystEngComm Pub Date : 2025-03-04 DOI:10.1039/D4CE01254B

D. O. Charkin, V. E. Kireev, N. A. Krupenikov, D. N. Dmitriev, D. A. Dorogov, S. M. Aksenov, K. A. Zagidullin, M. A. Volkov, A. P. Novikov, Iu. M. Nevolin, A. D. Krot, M. S. Grigoriev, E. G. Krivoborodov, A. V. Sitanskaia and I. G. Tananaev

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Abstract

We report the preparation, crystal structures, and non-covalent interaction analysis for a series of ammonium–18-crown-6 complex salts with tetrahedral monoanions, [(NH₄)(18C6)]⁺[TX₄]⁻·nH₂O, TX₄⁻ = BF₄⁻ (n = 0), TcO₄⁻ (n = 1), ReO₄⁻, OsO₃N⁻, CrO₃F⁻, CrO₃Cl⁻, and CrO₃Br⁻. In accordance with the size of the anion, the structures can be divided into several groups: “pseudo-dimeric anhydrous” {[NH₄(18C6)]₂(TX₄)}⁺[TX₄]⁻ for the tetrafluoroborate, monofluorochromate, and the previously reported perchlorate; “monomeric hydrate” for pertechnetate and nitridoosmate, and “monomeric anhydrous” for the perrhenate and the remaining monohalochromates. Thermal analysis was performed for compounds with different anion natures. The dependence of the complexes' thermal destruction temperature on the anion's oxidizing ability was shown. IR and MALDI analyses were performed for some complexes. The influence of crown ether on the processes of solubility and extraction of the pertechnetate anion in systems with organic solvents is shown.

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带四面体单阴离子的18-冠-6铵配合物：非共价相互作用的x射线、热分析和比较分析

我们报道了一系列具有四面体单阴离子的铵- 18-冠-6络合物的制备、晶体结构和非共价相互作用分析，[(NH4)(18C6)]+[TX4]−·nH2O, TX4−= BF4−(n = 0), TcO4−(n = 1), ReO4−,OsO3N−,CrO3F−，CrO3Cl−和CrO3Br−。根据阴离子的大小，结构可分为几类：“伪二聚体无水”{[NH4(18C6)]2(TX4)}+[TX4]−为四氟硼酸盐、单氟铬酸盐和先前报道的高氯酸盐；高氯酸盐和氮酸盐为“单体水合物”，高氯酸盐和剩下的单盐铬酸盐为“单体无水”。对不同阴离子性质的化合物进行了热分析。研究了配合物的热破坏温度与阴离子氧化能力的关系。对部分配合物进行IR和MALDI分析。研究了冠醚对高盐阴离子在有机溶剂体系中的溶解度和萃取过程的影响。

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