Synthesis, FT–IR characterization and crystal structure of aqua(5,10,15,20-tetraphenylporphyrinato-κ4N)manganese(III) trifluoromethanesulfonate

Abstract

In the title salt, [Mn(C44H28N4)(H2O)](CF3SO3) or [Mn(III)(TPP)(H2O)](CF3SO3) (where TPP is the dianion of 5,10,15,20-tetra-phenyl-porphyrin), the Mn(III) cation is chelated by the four pyrrole N atoms of the porphyrinate anion and additionally coordinated by an aqua ligand in an apical site, completing the distorted square-pyramidal coordination environment. The average Mn-N(pyrrole) bond length is 1.998 (9) Å and the Mn-O(aqua) bond length is 2.1057 (15) Å. The central Mn(III) ion is displaced by 0.1575 (5) Å from the N4C20 mean plane of the porphyrinate anion towards the apical aqua ligand. The porphyrinate macrocycle exhibits a moderate ruffling and strong saddle deformations. In the crystal lattice, the [Mn(III)(TPP)(H2O)](+) cation and the tri-fluoro-methane-sulfonate counter-ions are arranged in alternating planes packed along [001]. The components are linked together through O-H⋯O hydrogen bonds and much weaker C-H⋯O and C-H⋯F inter-actions. The crystal packing is further stabilized by weak C-H⋯π inter-actions involving the pyrrole and phenyl rings of the porphyrin moieties.