High-pressure structural studies of hematite<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi mathvariant="normal">Fe</mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:mrow><mml:mrow><mml:msub><mml:mrow><mml:mi mathvariant="normal">O</mml:mi></mml:mrow><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>

Structural studies and a full-profile refinement of the high-pressure phases of hematite $({\mathrm{Fe}}_{2}{\mathrm{O}}_{3})$ were carried out to 76 GPa using x-ray synchrotron powder diffraction. It was found that pressure induces a progressive distortion of the corundum-like hematite structure (HP1), culminating in a structural phase transition (HP2) at \ensuremath{\sim}50 GPa. At first sight the powder diffraction data obtained for HP2 could be equally explained in terms of either an orthorhombic perovskite or a ${\mathrm{Rh}}_{2}{\mathrm{O}}_{3}(\mathrm{II})$-type structure, but by a comparative analysis of the O-O bond length for both structures, recent M\"ossbauer spectroscopy results, and ab initio calculations allowed for the unambiguous assignment of the HP2 phase to the ${\mathrm{Rh}}_{2}{\mathrm{O}}_{3}(\mathrm{II})$-type structure. As a result of the phase transition the following changes are observed: (i) a substantial decrease in the Fe-O distances with a slight increase in Fe-Fe distances which led to a reduced cell volume, (ii) a diminution of the Fe-O-Fe bond distortion, and, (iii) a reduction in the distortion of the ${\mathrm{FeO}}_{6}$ octahedron. The structural transition coincides with a previously reported insulator-metal transition due to the electronic Mott transition. It is suggested that the unusual volume reduction of 10% is accounted by the combined crystallographic and electronic phase transition, the latter resulting into a substantial reduction of the ionic radii and consequently of the Fe-O bond lengths due to electron delocalization attributed to a charge-transfer gap closure. The mechanism of the combined structural, electronic, and magnetic transformations is discussed.