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-聚[[甲醇双氧铀(VI)]-μ-2-[5-(2-氧化苯基)-1,2,4-三唑-3-基]乙酸根-κ:']的晶体结构

Crystal structure of -poly[[methanoldioxidouranium(VI)]-μ-2-[5-(2-oxidophen-yl)-1-1,2,4-triazol-3-yl]acetato-κ :'].

作者信息

Vashchenko Oleksandr V, Khomenko Dmytro M, Doroshchuk Roman O, Stoica Alexandru-Constantin, Vassilyeva Olga Yu, Lampeka Rostyslav D

机构信息

Department of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 64/13, 01601 Kyiv, Ukraine.

Enamine Ltd. (www.enamine.net), Winston Churchill str. 78, 02094 Kyiv, Ukraine.

出版信息

Acta Crystallogr E Crystallogr Commun. 2024 Jul 12;80(Pt 8):852-856. doi: 10.1107/S2056989024006637. eCollection 2024 Aug 1.

Abstract

In the title complex, [U(CHNO)O(CHOH)] , the U cation has a typical penta-gonal-bipyramidal environment with the equatorial plane defined by one N and two O atoms of one doubly deprotonated 2-[5-(2-hy-droxy-phen-yl)-1-1,2,4-triazol-3-yl]acetic acid ligand, a carboxyl-ate O atom of the symmetry-related ligand and the O atom of the methanol mol-ecule [U-N/O 2.256 (4)-2.504 (5) Å]. The axial positions are occupied by two oxide O atoms. The equatorial atoms are almost coplanar, with the largest deviation from the mean plane being 0.121 Å for one of the O atoms. The benzene and triazole rings of the tetra-dentate chelating-bridging ligand are twisted by approximately 21.6 (2)° with respect to each other. The carboxyl-ate group of the ligand bridges two uranyl cations, forming a neutral zigzag chain reinforced by a strong O-H⋯O hydrogen bond. In the crystal, adjacent chains are linked into two-dimensional sheets parallel to the plane by C/N-H⋯N/O hydrogen bonding and π-π inter-actions. Further weak C-H⋯O contacts consolidate the three-dimensional supra-molecular architecture. In the solid state, the compound shows a broad medium intensity LMCT transition centred around 463 nm, which is responsible for its red colour.

摘要

在标题配合物[U(CHNO)O(CHOH)]中,铀阳离子具有典型的五角双锥环境,赤道平面由一个双去质子化的2-[5-(2-羟基苯基)-1,2,4-三唑-3-基]乙酸配体的一个氮原子和两个氧原子、对称相关配体的一个羧酸根氧原子以及甲醇分子的氧原子定义[U-N/O 2.256 (4)-2.504 (5) Å]。轴向位置由两个氧化物氧原子占据。赤道原子几乎共面,其中一个氧原子与平均平面的最大偏差为0.121 Å。四齿螯合桥联配体的苯环和三唑环彼此扭曲约21.6 (2)°。配体的羧酸根基团桥连两个铀酰阳离子,形成由强O-H⋯O氢键增强的中性锯齿链。在晶体中,相邻链通过C/N-H⋯N/O氢键和π-π相互作用连接成平行于平面的二维片层。进一步的弱C-H⋯O接触巩固了三维超分子结构。在固态下,该化合物在463 nm左右呈现出一个宽的中等强度的配体到金属离子电荷转移跃迁,这是其呈现红色的原因。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/99d6/11299739/5a6e5465f5bf/e-80-00852-fig1.jpg

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