New structural features of the high-pressure synthetic sheet-disilicate Phase-X, K(2–x)Mg2Si2O7Hx

Abstract 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 singlecrystal 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.