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(2,11-二氮杂-[3.3](2,6)吡啶环番-κ(4)N,N',N'',N''')(1,6,7,12-四氮杂苝-κ(2)N(1),N(12))钌(II)双(六氟磷酸根)乙腈1.422溶剂合物的晶体结构

Crystal structure of (2,11-di-aza-[3.3](2,6)pyridino-phane-κ (4) N,N',N'',N''')(1,6,7,12-tetra-aza-perylene-κ (2) N (1),N (12))ruthenium(II) bis-(hexa-fluorido-phosphate) aceto-nitrile 1.422-solvate.

作者信息

Brietzke Thomas, Rottke Falko Otto, Kelling Alexandra, Schilde Uwe, Holdt Hans-Jürgen

机构信息

Universität Potsdam, Institut für Chemie, Anorganische Chemie, Karl-Liebknecht-Str. 24-25, D-14476 Potsdam, Germany.

出版信息

Acta Crystallogr Sect E Struct Rep Online. 2014 Sep 30;70(Pt 10):265-8. doi: 10.1107/S1600536814021060. eCollection 2014 Oct 1.

Abstract

In the title compound, Ru(C14H16N4)(C16H8N4)2·1.422CH3CN, discrete dimers of complex cations, Ru(L-N4H2)tape are formed {L-N4H2 = 2,11-di-aza-3.3pyridino-phane; tape = 1,6,7,12-tetra-aza-perylene}, held together by π-π stacking inter-actions via the tape ligand moieties with a centroid-centroid distance of 3.49 (2) Å, assisted by hydrogen bonds between the non-coordinating tape ligand α,α'-di-imine unit and the amine proton of a 2,11-di-aza-3.3-pyridino-phane ligand of the opposite complex cation. The combination of these inter-actions leads to an unusual nearly face-to-face π-π stacking mode. Additional weak C-H⋯N, C-H⋯F, N-H⋯F and P-F⋯π-ring (tape, py) (with F⋯centroid distances of 2.925-3.984 Å) inter-actions are found, leading to a three-dimensional architecture. The Ru(II) atom is coordinated in a distorted octa-hedral geometry, particularly manifested by the Namine-Ru-Namine angle of 153.79 (10)°. The counter-charge is provided by two hexa-fluorido-phosphate anions and the asymmetric unit is completed by aceto-nitrile solvent mol-ecules of crystallization. Disorder was observed for both the hexa-fluorido-phosphate anions as well as the aceto-nitrile solvate mol-ecules, with occupancies for the major moieties of 0.801 (6) for one of the PF6 anions, and a shared occupancy of 0.9215 (17) for the second PF6 anion and a partially occupied aceto-nitrile mol-ecule. A second CH3CN mol-ecule is fully occupied, but 1:1 disordered across a crystallographic inversion center.

摘要

在标题化合物Ru(C₁₄H₁₆N₄)(C₁₆H₈N₄)₂·1.422CH₃CN中,形成了由复杂阳离子Ru(L-N₄H₂)tape组成的离散二聚体{L-N₄H₂ = 2,11-二氮杂-3.3吡啶并环番;tape = 1,6,7,12-四氮杂苝},通过π-π堆积相互作用经由tape配体部分连接在一起,质心间距为3.49(2) Å,同时在非配位的tape配体α,α'-二亚胺单元与相反复杂阳离子的2,11-二氮杂-3.3吡啶并环番配体的胺质子之间存在氢键辅助。这些相互作用的组合导致了一种不寻常的近乎面对面的π-π堆积模式。还发现了额外的弱C-H⋯N、C-H⋯F、N-H⋯F和P-F⋯π环(tape、py)(F⋯质心距离为2.925 - 3.984 Å)相互作用,形成了三维结构。Ru(II)原子以扭曲的八面体几何构型配位,尤其体现在N胺-Ru-N胺角度为153.79(10)°。抗衡电荷由两个六氟磷酸根阴离子提供,不对称单元由结晶的乙腈溶剂分子完成。观察到六氟磷酸根阴离子以及乙腈溶剂分子均存在无序现象,其中一个PF₆阴离子主要部分的占有率为0.801(6),第二个PF₆阴离子和一个部分占据的乙腈分子的共享占有率为0.9215(17)。第二个CH₃CN分子被完全占据,但在一个晶体学反演中心处存在1:1无序。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dc8b/4257199/b71497d89683/e-70-00265-fig1.jpg

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