Unusual M (super 3+) cations in synthetic amphiboles with nominal fluoro-eckermannite composition; deviations from stoichiometry and structural effects of the cummingtonite component

Single-crystal structure-refinement and electron-microprobe analysis of synthetic amphiboles with nominal fluoro-eckermannite composition and different trivalent cations (Al, Sc, Ti (super 3+) , V (super 3+) , Cr (super 3+) , Ga,) show significant deviations from nominal stoichiometry. Synthetic Sc- and Cr-bearing fluoro-eckermannite are close to nominal stoichiometry, whereas the corresponding nominal Al-, V (super 3+) -, Ga-, and Ti-bearing species contain very few trivalent cations and approximate Na(NaMg)Mg 5 Si 8 O 22 F 2 , a composition that has not been found in natural systems. The presence of a significant cummingtonite component strongly affects unit-cell parameters, coordination geometry around the B-, C-, and T-group sites, and cation ordering at the A-group sites. The high-charge cations are completely ordered at the M2 site, and there is a well-developed linear relationship between "M2-O" and the constituent-cation radius at the M2 site. The synthetic fluoro-eckermannite structure is stabilized by large spherically symmetric trivalent cations at the M2 site; for small spherically symmetric trivalent cations, it is not stable (at least at the synthesis conditions used here). Synthetic chromium-fluoro-eckermannite is stabilized by the non-spherically symmetric 3d 3 electronic arrangement, whereas Ga and V (super 3+) (3d 2 ) do not stabilize the fluoroeckermannite structure.