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包含全氟羧酸银(I)立方八面体簇和双(甲硫基)甲烷配体的一维配位聚合物。

One-dimensional coordination polymers incorporating silver(I) perfluorocarboxylate cuboctahedral clusters and the bis(methylthio)methane ligand.

作者信息

Awaleh Mohamed Osman, Badia Antonella, Brisse François

机构信息

Département de Chimie, Université de Montréal, C.P. 6128, Succursale Centre-ville, Québec, Canada H3C 3J7.

出版信息

Inorg Chem. 2007 Apr 16;46(8):3185-91. doi: 10.1021/ic062232q. Epub 2007 Mar 16.

Abstract

Two topologically comparable complexes, [Ag6(CF3CO2)3(L1-Me)3(SCH3)3]infinity (1) and [Ag6(CF3CF2CO2)3(L1-Me)2(SCH3)3(H2O)]infinity (2), were prepared and characterized by single-crystal diffractometry. The structures consist of Ag12S6 clusters linked by bis(methylthio)methane ligands, L1-Me, thus forming 1D coordination polymers. The 12 Ag atoms of the cluster are situated at the corners of a distorted cuboctahedron. The sulfur atoms of the six mu4-SCH3 entities occupy a position approximately 0.8 A above the center of each of the square faces of the polyhedron. The cleavage of the C-S bond of some of the ligands occurs during the syntheses, producing the -SCH3 anions. The coordination of the silver atoms varies from 5 to 7. The Ag...Ag contacts range from 2.9250(5) to 3.3615(6) A and from 2.961(1) to 3.380(1) A for 1 and 2, respectively. A polymeric ribbon is obtained when four ligands link a given cluster to two others. The chains of 1, held only by van der Waals forces, pack in a hexagonal manner. The two water molecules in 2 (Ag-OH2 = 2.385(7) A) are coordinated to silver atoms of the cluster. They are also strongly hydrogen bonded to the oxygen atoms of two pentafluoropropionate groups, one within the cluster (O...O = 2.741(1) A), the other in an adjacent chain (O...O = 2.818(1) A). The chains, thus H bonded to one another, generate a 2D coordination network.

摘要

制备了两种拓扑结构可比的配合物,即无限长链状的[Ag6(CF3CO2)3(L1-Me)3(SCH3)3](1)和[Ag6(CF3CF2CO2)3(L1-Me)2(SCH3)3(H2O)](2),并通过单晶衍射法对其进行了表征。其结构由通过双(甲硫基)甲烷配体L1-Me连接的Ag12S6簇组成,从而形成一维配位聚合物。簇中的12个银原子位于一个扭曲的立方八面体的角上。六个μ4-SCH3实体的硫原子占据多面体每个正方形面中心上方约0.8 Å的位置。在合成过程中,一些配体的C-S键发生断裂,生成-SCH3阴离子。银原子的配位数从5到7不等。对于1和2,Ag…Ag接触距离分别在2.9250(5)至3.3615(6) Å和2.961(1)至3.380(1) Å之间。当四个配体将一个给定的簇与另外两个簇相连时,可得到一个聚合物带。仅通过范德华力维系的1的链以六方方式堆积。2中的两个水分子(Ag-OH2 = 2.385(7) Å)与簇中的银原子配位。它们还与两个五氟丙酸酯基团的氧原子形成强氢键,一个在簇内(O…O = 2.741(1) Å),另一个在相邻链中(O…O = 2.818(1) Å)。因此,这些链彼此通过氢键相连,形成二维配位网络。

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