Awaleh Mohamed Osman, Badia Antonella, Brisse François
Département de Chimie, Université de Montréal, C.P. 6128, Succursale Centre-ville, Québec, Canada H3C 3J7.
Inorg Chem. 2007 Apr 16;46(8):3185-91. doi: 10.1021/ic062232q. Epub 2007 Mar 16.
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.
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。