X-ray Structure Refinement and Vibrational Spectroscopy of Metavauxite FeAl₂(PO₄)₂(OH)₂·8H₂O

Abstract

In this paper, we provide a crystal-chemical investigation of metavauxite, ideally FeAl2(PO4)2(OH)2·8H2O, from Llallagua (Bolivia) by using a multi-methodological approach based on EDS microchemical analysis, single crystal X-ray diffraction, and Raman and Fourier transform infrared (FTIR) spectroscopy. Our new diffraction results allowed us to locate all hydrogen atoms from the structure refinements in the monoclinic P21/c space group. Metavauxite structure displays a complex framework consisting of a stacking of [Al(PO4)3(OH)(H2O)2]7− layers linked to isolated [Fe(H2O)6]2+ cationic octahedral complex solely by hydrogen bonding. The hydrogen-bonding scheme was inferred from bond-valence calculations and donor-acceptor distances. Accordingly, strong hydrogen bonds, due to four coordinated H2O molecules, bridge the [Fe(H2O)6]2+ units to the Al/P octahedral/tetrahedral layer. The hydroxyl group, coordinated by two Al atoms, contributes to the intra-layer linkage. FTIR and Raman spectra in the high-frequency region (3700−3200 cm−1) are very similar, and show a complex broad band consisting of several overlapping components due to the H2O molecules connecting the isolated Fe(H2O)6 and the adjacent Al/P octahedral/tetrahedral layers. A sharp peak at 3540 cm−1 is assigned to the stretching mode of the OH group. The patterns collected in the low-frequency region are dominated by the stretching and bending modes of the PO43− group and the metal-oxygen polyhedra.

Keywords

• metavauxite
• phosphate
• single-crystal X-ray structure refinement
• hydrogen bonding network
• FTIR and Raman spectroscopy