Polymere Iodoplumbate – Synthese und Kristallstrukturen von (Pr3N–C2H4–NPr3)[Pb6I14(dmf)2] · 4 DMF, (Pr3N–C2H4–NPr3)[Pb(dmf)6][Pb5I14] · DMF und (Me3N–C2H4–NMe3)2[Pb2I7]I

Polymeric Iodoplumbates – Synthesis and Crystal Structures of (Pr₃N–C₂H₄–NPr₃)Pb₆I₁₄(dmf)₂] · 4 DMF, (Pr₃N–C₂H₄–NPr₃)Pb(dmf)₆]Pb₅I₁₄] · DMF, and (Me₃N–C₂H₄–NMe₃)₂Pb₂I₇]I (Pr₃N–C₂H₄–NPr₃)Pb₆I₁₄(dmf)₂] · 4 DMF ( 1 ) and (Pr₃N–C₂H₄–NPr₃)Pb(dmf)₆]Pb₅I₁₄] · DMF ( 2 ) have almost the same composition, but completely different structures. Both compounds are formed selectively depending on the reaction and crystallization conditions. In 2 the Pb^II atoms are coordinated either by six bridging I^– ligands in the two-dimensional Pb₅I₁₄]^4– network or by six DMF ligands in the Pb(dmf)₆]²⁺ cations. In contrast, (Me₃N–C₂H₄–NMe₃)₂Pb₂I₇]I ( 3 ) contains non-coordinating I^– anions between the iodoplumbate layers. The iodoplumbate anions in 2 and 3 consist of face and corner sharing PbI₆ octahedra, whereas in 1 PbI₆ and PbI₅(dmf) octahedra share common edges to form a one-dimensional polymeric section of the PbI₂ structure. (Pr₃N–C₂H₄–NPr₃)Pb₆I₁₄(dmf)₂] · 4 DMF ( 1 ): Space group P1, a = 920.1(3), b = 1597.2(5), c = 1613.9(4) pm, α = 66.02(2), β = 84.53(2), γ = 85.99(2)°, V = 2156(1) · 10⁶ pm³; (Pr₃N–C₂H₄–NPr₃)Pb(dmf)₆]Pb₅I₁₄]·DMF ( 2 ): Space group P2₁, a = 1201.21(9), b = 3031.1(2), c = 1294.96(9) pm, β = 108.935(7)°, V = 4459.8(5) · 10⁶ pm³; (Me₃N–C₂H₄–NMe₃)₂Pb₂I₇]I ( 3 ): Space group Pnma, a = 2349.9(2), b = 1623.83(9), c = 980.75(7) pm, V = 3742.4(5) · 10⁶ pm³.