Polymeric structure of a coproporphyrin I ruthenium(II) complex: a powder diffraction study

Porphyrin complexes of ruthenium are widely used as models for the heme protein system, for modelling naturally occurring iron–porphyrin systems and as catalysts in epoxidation reactions. The structural diversity of ruthenium complexes offers an opportunity to use them in the design of multifunctional supramolecular assemblies. Coproporphyrins and metallocoproporphyrins are used as sensors in bioassay and the potential use of derivatives as multiparametric sensors for oxygen and H+ is one of the main factors driving a growing interest in the synthesis of new porphyrin derivatives. In the coproporphyrin I RuII complex catena‐poly[[carbonylruthenium(II)]‐μ‐2,7,12,17‐tetrakis[2‐(ethoxycarbonyl)ethyl]‐3,8,13,18‐tetramethylporphyrinato‐κ5N,N′,N′′,N′′′:O], [Ru(C44H52N4O8)(CO)]n, the RuII centre is coordinated by four N atoms in the basal plane, and by axial C (carbonyl ligand) and O (ethoxycarbonylethyl arm from a neighbouring complex) atoms. The complex adopts a distorted octahedral geometry. Self‐assembly of the molecules during crystallization from a methylene chloride–ethanol (1:10 v/v) solution at room temperature gives one‐dimensional polymeric chains. The crystal structure of the coproporphyrin I RuII complex catena‐poly[[carbonylruthenium(II)]‐μ‐2,7,12,17‐tetrakis[2‐(ethoxycarbonyl)ethyl]‐3,8,13,18‐tetramethylporphyrinato] has been determined from high‐resolution synchrotron powder diffraction data. The RuII centre is coordinated by four N atoms in a basal plane, and by axial C and O atoms in a distorted octahedral geometry. Self‐assembly of the molecules during crystallization gives one‐dimensional polymeric chains.