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一种具有硫酸氢根抗衡阴离子的一维碘桥联铂/铂混合价态络合阳离子。

A one-dimensional iodido-bridged Pt/Pt mixed-valence complex cation with a hydrogen sulfate counter-anion.

作者信息

Matsushita Nobuyuki

机构信息

Department of Chemistry & Research Center for Smart Molecules, Rikkyo University, Nishi-Ikebukuro 3-34-1, Toshima-ku, 171-8501 Tokyo, Japan.

出版信息

Acta Crystallogr E Crystallogr Commun. 2018 Nov 22;74(Pt 12):1821-1825. doi: 10.1107/S2056989018016158. eCollection 2018 Dec 1.

Abstract

The title compound, -poly[[[bis-(ethyl-enedi-amine-κ ,')platinum(II)]-μ-iodido-[bis-(ethyl-enedi-amine-κ ,')platinum(IV)]-μ-iodido] tetra-(hydrogen sulfate) dihydrate], {[Pt(CHN)]PtI(CHN)·2HO} , has a linear chain structure comprising alternating platinum cations with mixed-valent oxidation states of +II/IV. Square-planar [Pt(en)] cations and elongated octa-hedral -[PtI(en)] cations (en is ethyl-enedi-amine) are stacked alternately parallel to the axis, and are bridged by the I ligands. The Pt site of the [Pt(en)] units is located on a twofold rotation axis. The I site, which is located on the same twofold rotation axis, is equally disordered over two positions. The Pt and I sites form a straight ⋯I-Pt-I⋯Pt⋯ chain, with Pt-I bond lengths of 2.7202 (6) and 2.6917 (6) Å, and Pt⋯I contacts of 3.2249 (6) and 3.2534 (6) Å. The mixed-valence state of the Pt site is expressed by the structural parameter = (Pt-I)/(Pt⋯I), with values of 0.843 and 0.827 for the two independent I atoms. In the crystal structure, the cationic columnar structure is stabilized by hydrogen bonds of the type N-H⋯O between the amine groups of the Pt complex chains and the disordered hydrogen sulfate counter anions, and between the amine groups and water mol-ecules of crystallization. In addition, O-H⋯O hydrogen bonds between the hydrogen sulfate anions and water mol-ecules of crystallization and between the hydrogen sulfate anions themselves consolidate the crystal packing.

摘要

标题化合物,-聚[[[双-(乙二胺-κ,')铂(II)]-μ-碘代-[双-(乙二胺-κ,')铂(IV)]-μ-碘代]四-(硫酸氢盐)二水合物],{[Pt(CHN)]PtI(CHN)·2HO} ,具有线性链结构,由具有 +II/IV 混合价态的交替铂阳离子组成。平面正方形的[Pt(en)]阳离子和拉长八面体的-[PtI(en)]阳离子(en 为乙二胺)沿 轴交替平行堆叠,并由 I 配体桥连。[Pt(en)]单元的 Pt 位点位于二重旋转轴上。位于同一二重旋转轴上的 I 位点在两个位置上同等无序。Pt 和 I 位点形成一条直的⋯I-Pt-I⋯Pt⋯链,Pt-I 键长为 2.7202 (6) 和 2.6917 (6) Å,Pt⋯I 接触距离为 3.2249 (6) 和 3.2534 (6) Å。Pt 位点的混合价态由结构参数 = (Pt-I)/(Pt⋯I)表示,两个独立的 I 原子的值分别为 0.843 和 0.827。在晶体结构中,阳离子柱状结构通过 Pt 络合物链的胺基与无序的硫酸氢根抗衡阴离子之间以及胺基与结晶水分子之间的 N-H⋯O 型氢键得以稳定。此外,硫酸氢根阴离子与结晶水分子之间以及硫酸氢根阴离子自身之间的 O-H⋯O 氢键巩固了晶体堆积。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eeae/6281129/58f828efc188/e-74-01821-fig1.jpg

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