The structure of hibonite from Myanmar (space group P63/mmc, Z = 2, at room temperature a = 5.5909(1), c = 21.9893(4)Å), with simplified formula CaAl12O19 and composition (Ca0.99Na0.01)Σ1.00 (Al10.74Ti0.52 Mg0.51Zn0.11Si0.08

)Σ12.00O18.97, was investigated between temperatures of 100 K and 923 K by single-crystal X-ray diffraction methods. Structure refinements have been performed at 100, 296, 473 and 923 K. In hibonite from Myanmar, Ti substitutes for Al mainly at the octahedral Al4 site and, to a lesser degree, at the trigonal bipyramidal site, Al2. The Al4 octahedra build face-sharing dimers. If Ti4+ substitutes at Al4, adjacent cations repulse each other for electrostatic reasons, leading to off-centre cation displacement associated with significant bond-length distortion compared to synthetic (Ti-free) CaAl12O19. Most Mg and smaller proportions of Zn and Si are assigned to the tetrahedral Al3 site. 12-coordinated Ca in hibonite replaces oxygen in a closest-packed layer. However, Ca is actually too small for this site and engages in a `rattling-type' motion with increasing temperature. For this reason, Ca does not significantly increase thermal expansion coefficients of hibonite. The expansion of natural Ti,Mg-rich hibonite between 296 and 923 K along the x and the z axes is αa = 7.64 × 10−6 K−1 and αc = 11.19 × 10−6 K−1, respectively, and is thus very similar to isotypic, synthetic CaAl12O19 and LaMgAl11O19 (LMA).

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