Space group and hydrogen positions of single crystal delta-AlOOH, (Al0.84Mg0.07Si0.09)H0.98O2 and its relation to stishovite and brucite

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A single crystal of δ-AlOOH synthesized by Suzuki et al. (2000) at conditions of 1000^oC and 21 GPa was used in this study. A set of X-ray diffraction intensities up to sinθ/λ=0.80 Å-1 were measured with a single crystal of 83×35×24 μm using MoKα radiation (50 kV, 40 mA). Al:Mg:Si ratio 0.84:0.07:0.09 measured by EDS with the same crystal used in the X-ray diffraction intensity measurement yielded the chemical formula (Al0.84Mg0.07Si0.09)H0.98O_2. Suzuki et al. (2000) reported the space group P2_1nm from powder X-ray data but the systematic absence of reflections observed in this study indicated another space group Pnn2. The systematic absence of reflections observed in the present work were h+l odd for h0l and k+l odd for 0kl, indicating possible space group Pnn2 or Pnnm. The N(Z) test for a center of symmetry indicated an acentric space group. The non-centrosymmetric space group Pnn2 was therefore employed and was confirmed by the structural refinement. The agreement factors for 109 independent reflections (Io>= 3.0σ Io) were R=3.6% with anisotropic temperature factors. The difference Fourier synthesis was calculated and two significant Fourier peaks H1 and H2 for the possible hydrogen sites were found. The H1 site locates around two-fold rotation axis with H1-H1 distance of 0.55 Å. The H1 site is considered to be for symmetrical statistical distribution of hydrogen atoms. The H2-H2 are separated with H2-H2 distance 2.12 Å which is larger than the sum of van der Waals radii of hydrogen atoms. The partial occupancy of Mg and Si atoms at Al site suggests the possibility of limited solid solution among δ-AlOOH, stishovite SiO_2 and hypothetical rutile-structured Mg(OH)_2. The H1 site is considered to be for AlOOH and the H_2 site for Mg(OH)_2.

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