Crystal chemical characterization and computational modeling of a μ-oxo Fe(III) complex with 1,10-phenanthroline clarify its interaction and reactivity with montmorillonite

This work provides a systematic study of the mu-oxo-di-fac-[triaqua-(1,10-phenanthroline-kappa(2) N,N')-iron(III)]bis(sulfate), [(OH2)(3)(phen)FeOFe(phen)(OH2)(3)] (SO4)(2) (phen = phenanthroline). Crystal structure is determined by single-crystal X-ray diffraction data and refined to R = 0.039. The crystal structure is monoclinic (Z = 2), space group P2(1) with unit cell dimensions a = 8.5157(3), b = 17.6434(5), c = 9.9678(3) angstrom, beta = 90.133(2)degrees, V = 1497.62(8) angstrom(3). The triaqua(1,10-phenanthroline)iron(III) parts are linked through one oxo-bridge. Both Fe(III) cations show a distorted octahedral coordination. The single-crystal data are complemented by computational chemistry modeling at quantum mechanical level, X-ray powder diffraction at room and high temperature conditions and by thermal analysis. Molecular modeling suggests that the role of the crystallization water molecules is critical to establish the intermolecular interactions for the stability of the crystal structure.