Bismuth(III) Anthranilates – Synthesis and Characterization of a Coordination Polymer and a Polynuclear Oxido Cluster

Abstract

Bismuth carboxylates of the composition Bi(anth)3·Solv (1a: Solv = 0.5MeNO2·0.5H2O, 1b: Solv = 0.5MeCN) were isolated from the reaction of BiPh3 with three equivalents of anthranilic acid (Hanth, 2‐aminobenzoic acid) in nitromethane and acetonitrile, respectively. The composition of the soluble compounds 1a and 1b was established by NMR and infrared spectroscopy, and elemental analysis. The thermal behavior was evaluated by thermogravimetric analysis (TGA), and bismuth oxide and bismuth were observed as final decomposition products in air and helium, respectively. Both compounds 1a and 1b crystallize in the monoclinic space group P21/n with formation of a one‐dimensional coordination polymer of Bi–N‐bridged dimers, which crystallize with non‐coordinating solvent molecules to give [Bi(anth)3·Solv]∞, as was shown by single‐crystal X‐ray diffraction analysis. The reaction of [Bi6O4(OH)4(NO3)6]·H2O with anthranilic acid resulted in the polynuclear bismuth oxido anthranilato nitrate [{Bi38O45(anth)4(NO3)20(DMSO)24}{Bi38O45(anth)4(NO3)20(DMSO)24}]·6DMSO (2) upon crystallization from DMSO. Compound 2 crystallizes in the triclinic space group P1 with two crystallographically independent molecules in the asymmetric unit and represents the first example of a bismuth oxido cluster bearing anthranilate ligands.