The crystal structure determination and redefinition of matulaite, Fe3+Al7(PO4)4(PO3OH)2(OH)8(H2O)8·8H2O

Abstract

AbstractMatulaite was first described by Moore and Ito (1980) from the Bachman mine, Hellertown, Northampton County, Pennsylvania, USA. Its ideal formula was reported as CaAl18(PO4)12(OH)20·28H2O, based on wet-chemical analysis. Re-examination of both existing cotype specimens of matulaite revealed no material matching the powder or single-crystal X-ray diffraction data reported for the species. Other samples examined from the type locality, as well as from the LCA pegmatite in North Carolina, USA, and Fumade, Tarn, France, provided material crystallographically consistent with matulaite: P21/n, a = 10.604(2), b = 16.608(4), c = 20.647(5) Å , b = 98.848(7)° and Z = 4. Electron microprobe and crystal structure analysis of newly studied material from the type locality showed the ideal formula of matulaite to be Fe3+ Al7(PO4)4(PO3OH)2(OH)8(H2O)8˙8H2O. The chemical composition reported by Moore and Ito (1980) was most probably determined on a mixture of mostly kobokoboite and afmite, with lesser amounts of crandallite. As there is no matulaite on any of the existing cotype specimens of the species, the two specimens used to obtain the new chemical analyses, powder and single-crystal X-ray diffraction data and the structure determination are designated as neotypes. The neotypes have also been used to obtain crystal morphology and new measurements of the physical and optical properties of the species. The neotypes and new data have been approved by the CNMNC, proposal 11-F. The crystal structure of matulaite contains seven-member chain segments of AlO6 octahedra decorated by PO4 tetrahedra. The PO4 tetrahedra also link to isolated FeO6 octahedra, resulting in a 'pinwheel' Fe(PO4)6 group. The linkage of octahedra and tetrahedra defines a thick layer parallel to {001}. The only linkage between layers is via hydrogen bonding to interlayer water molecules.