Ellenbergerite,a new high-pressure Mg-Al-(Ti,Zr)-silicate with a novel structure based on face-sharing octahedra

Ellenbergerite occurs as purple millimetre-size grains associated with talc, kyanite, clinochlore, rutile, and zircon in composite inclusions within decimetre-large pyrope crystals (90–98 mole percent end-member) in the quartzite layer of the Dora Maira massif, Western Alps, from which coesite has been recently reported (Chopin 1984). It is hexagonal, a=12.255(8), c=4.932(4) Å, Z=1, space group P6₃. Mohs hardness 6.5; D_mes 3.15, D_cal 3.10; no cleavage. Uniaxial negative and vividly pleochroic, colourless, colourless to deep lilac with colour zoning. The intensely coloured variety has 1.6789(5), 1.670(1); microprobe analysis yields SiO₂ 39.1, P₂O₅ 0.45, Al₂O₃ 25.1, TiO₂ 4.0, MgO 22.2, FeO 0.20, sum 99.05 wt.% including H₂O 8.0 (coulometrically). The formula calculated on a O₂₈(OH)₁₀ basis (implying 7.5 wt.% H₂O) is Mg_6.71 Fe_0.03 Ti_0.61 Al_6.00 Si_7.92 P_0.08 O₂₈(OH)₁₀ The colour zoning is due to nearly complete TiZr substitution. In addition ellenbergerite may contain more than 8 wt.% P₂O₅ with strictly correlated changes of Si, Mg, Al and Ti+Zr contents, over 80% of which represent the SiAlPMg substitution.The structure has been determined from 1049 observed independent reflections and refined to R=0.034, R_w=0.031, including six of ten protons. It consists of single chains of face-sharing octahedra with one third vacancies extending along the six-fold screw axes, and of pairs of fully occupied face-sharing octahedra linked by edge-sharing to form octahedral double chains parallel to the twofold screw axes, all interconnected by SiO₄ tetrahedra. It may be compared with the dumortierite polymorph with space group P6₃mc derived hypothetically by Moore and Araki (1978). The structural formula is (Mg,Ti,Zr,)₂ Mg₆(Al,Mg)₆ (Si,P)₂ Si₆ O₂₈(OH)₁₀ Face-sharing octahedra are an unusual feature in silicates which results in a dense structure and reflects, considering the common bulk composition, the uncommon high-pressure formation conditions (about 25–30 kbar, 700–800° C). Ti⁴⁺-Fe²⁺ charge transfer between face-sharing octahedra on the six-fold screw axes most likely accounts for the absorption scheme.