Discrete and polymeric iodoplumbates with Pb3I10 building blocks: [Pb3I10]4−, [Pb7I22]8−, [Pb10I28]8−, 1∞[Pb3I10]4− and 2∞[Pb7I18]4−

Iodoplumbate complexes were obtained by reaction of PbI2 with sodium iodide in polar organic solvents and precipitation with large cations. With diammonium cations [R3N(CH2)nNR3]2+ a series of polynuclear iodoplumbates could be isolated and characterized by single crystal X-ray diffraction. While [Bu3N(CH2)4NBu3]2[Pb3I10] 1, [Bu3N(CH2)4NBu3]4[Pb7I22] 2 and [Bu3N(CH2)4NBu3]4[Pb10I28] 3 contain discrete anions, the iodoplumbates [Me3N(CH2)5NMe3]2[Pb3I10] 4 and [Pr3N(CH2)5NPr3]2[Pb7I18] 5 consist of one-dimensional and two-dimensional co-ordination polymers, respectively. The [Pb3I10]4– anion in 1 can be regarded as a building block for the structures of 2, 4, 5 and, slightly modified, of 3. In spite of their related structures and similar compositions, these complexes are formed selectively and in good yield under appropriate reaction and crystallization conditions.