In this contribution, we investigate, by means of Density Functional Theory computations coupled to the analysis of the Electron Localisation Function ( ELF), a new possible topology of the Pb2+ valence lone pair. The possibility of bisdirectionality is uncovered for the first time and reveals another character of lead complexes beyond holo/hemidirectionality. (C) 2009 Elsevier B. V. All rights reserved.