The structure of the synthetic high-pressure sheet-disilicate Phase-X (PhX), a possible host of H2O and K in the mantle, has been determined for a crystal synthesized at 16 GPa/1300 °C/23 h. The composition of the sample is close to K1.5Mg2Si2O7H0.5, which is 50% PhX/50% Anhydrous-PhX and has 25% of interlayer K sites vacant. The structures of four crystals were determined by single-crystal X-ray diffraction and had very similar diffraction characteristics and structural results; the structure of one of the larger crystals is reported here. Reflection intensity statistics strongly indicate that PhX is centrosymmetric, space group P63/mcm, in contrast to other studies that have reported non-centrosymmetric space group P63cm. While it was possible to obtain good agreement indices for refinements in P63cm, there were strong correlations between atoms that are equivalent in P63/mcm, suggesting that the correct structure is centrosymmetric. Full anisotropic refinement in space group P63/mcm gave R1 = 0.036, wR2 = 0.079, GoF = 1.467. As with all previous studies of PhX, the H atom was not located. Difference-Fourier maps of the residual electron density indicated that the K atom is displaced from the 4c site lying on the sixfold axis on to three split 12j sites 0.2 Å away, each having ¼ occupancy, giving a total of 3 K atoms per unit cell and corresponding to 1.5 K apfu, in good agreement with the content derived from electron microprobe analysis. Diffraction patterns of all four crystals examined, reconstructed from the full-intensity data collection, consistently show the presence of a large hexagonal superstructure with dimensions 8asub × 8asub × csub, having Z = 128, compared with Z = 2 for the two-layer subcell. Complex arrays of superlattice reflections occur in layers with l = 2n, but are absent from l = 2n + 1 layers.

Unpolarized infrared spectra of single crystals of PhX were obtained that are similar to those reported previously in the literature. Spectra in the OH-stretching region consist of a major absorption band at 3595 cm−1 and three much weaker bands at 3690, 3560, and 3405 cm−1. Bond-valence analysis of PhX indicates that O1 is very over-bonded, whereas O2 is slightly under-bonded and a possible site for protonation. We present geometrical and crystal-chemical arguments that exclude O1 as a candidate for protonation, whereas a much better case can be made for O2. In PhX structures, H must be located at a partially occupied site with a multiplicity 4 ≤ m ≤ 24 in P63/mcm or 4 ≤ m ≤ 12 in P63cm. Such low occupancies for H sites are the likely reason for their invisibility to diffraction. We outline a model for the incorporation of H into PhX of composition K1.5Mg2Si2O7H0.5 that suggests a mechanism for ordering based upon avoidance of H and K, coupled with K-site vacancies. Such behavior may also be the origin of the superstructure. The P63/mcm structure and the presence of an underlying superstructure may well be characteristic of ordered intermediate compositions at or near PhX50/Anhydrous-PhX50. Identification of a new space group and recognition of a previously unobserved superstructure point to new possibilities for PhX and its derivatives that may bear significantly upon their stability at mantle conditions.

You do not currently have access to this article.