One-dimensional infinite iodoplumbates with new structural types have been prepared by crystallization from solutions containing PbI2 and NaI with large counter ions. Whereas [(PhCH2)4P]2[Pb3I8] 1 contains PbII with octahedral and square pyramidal coordination, in [Me3N(CH2)6NMe3][PbI3]22, [Na(dmf)3]4[Pb6I16] 3, [Na4(dmf)14][PbI3]44, [PrN(C2H4)3NPr][Pb2I6] 5 and [Bu3N(CH2)2NBu3]2[Pb10I24] 6 all Pb atoms are six-coordinated. The great structural variety of these compounds is achieved by condensation of PbI6 octahedra in several different ways. Face-sharing octahedra are observed in 2 and 4, edge-sharing octahedra characterize the anionic substructure of 6. In the iodoplumbates 3 and 5 PbI6 octahedra share common faces, edges and vertices at the same time. The Pb–I distances ranging from 293.5 to 364.5 pm can be explained on the basis of different degrees of bridging of the iodo ligands and the trans influence of ligands in trans position. The composition and structure of the iodoplumbate anions are mainly determined by the size, shape and charge of the counter ions used for crystallization.
通过从含有大反离子的 PbI2 和 NaI 的溶液中结晶制备出了具有新结构类型的一维无限
碘铂酸盐。在[(Ph )4P]2[Pb3I8]1 中,PbII 具有八面体和正方形
金字塔配位,而在[Me3N(
CH2)6NMe3][PbI3]22 中,PbII 具有八面体和正方形
金字塔配位、[Na(dmf)3]4[Pb6I16]3、[Na4(dmf)14][PbI3]44、[PrN(
C2H4)3NPr][Pb2I6]5 和 [Bu3N( )2NBu3]2[Pb10I24] 6 中,所有的
铅原子都是六配位的。PbI6 八面体通过几种不同的缩合方式实现了这些化合物结构的多样性。在 2 和 4 中可以观察到共面八面体,共边八面体是 6 的阴离子子结构的特征。Pb-I 间距从 293.5 到 364.5 pm 不等,这可以根据
碘配体不同的桥接程度和
配体在反式位置的反式影响来解释。
碘铂酸阴离子的组成和结构主要取决于结晶时所用的反离子的大小、形状和电荷。