A crystal chemical study of protoanthophyllite: Orthoamphiboles with the protoamphibole structure

Abstract

Two new protoamphibole-type amphiboles with space group type Pnmn, have been found in nature: protoferro-anthophyllite (Fe0.80Mn0 20)2 (Fe0 98Mg0.02)5 (Si4O11)2(OH)2, and protomangano-ferro-anthophyllite, (Mn0 70Fe0.30)2 (Fe0.82Mg0 18)5 (Si4O11)2(OH)2. Protoferro-anthophyllite (PFA) occurs in pegmatites at both Gifu Prefecture, Japan and at Cheyenne Mountain, El Paso County, Colorado, USA. Protomangano-ferro-anthophyllite, (PMFA) occurs in pegmatites at Fukushima Prefecture and in a Mn mine at Tochigi Prefecture, Japan. Structure determinations of the two amphiboles show that both are isostructural with the synthetic fluorian-amphibole, protoamphibole (= protofluorian-lithian-anthophyllite). A calculation of the procrystal electron density distributions, the bond paths and the bond critical point properties of PFA, PMFA, grunerite and protoamphibole indicates that the M4 cation in these amphiboles is 4-coordinated. A calculation of the electron density distributions at the Becke3LYP/6-311G(2d,p) level for model silicate tetrahedra for these amphiboles and anthophyllite reveals that the value of the electron density at the bond critical points, ρ(rc), for the SiO(nbr) bonds is larger, on average (0.93 e/Å3), than that for the SiO(br) bonds (0.90 e/Å3). The observed SiO bond lengths decrease linearly with increasing ρ(rc) while the magnitudes of the curvatures of ρ(rc) both perpendicular and parallel to the bonds and the Laplacian of ρ(rc) each increases. These trends are associated with an increase in the electronegativity of the S1 cation, a possible increase in the covalent character of the SiO bond and a tendency for SiO(nbr) bonds to be involved in wider OSiO angles than SiO(br) bonds. It is possible, if not likely, that protoanthophyllite has often been misidentified as anthophyllite.