Crystal structure of a new chain diborate TmH[B2O5] and its comparison with related compound GdH[B2O5] based on the pseudosymmetry and the group-subgroup relation

Abstract

Crystals of a new rare-earth chain diborate TmH[B2O5], space group C2/c, are obtained under hydrothermal conditions. The structure is determined without preliminary knowledge of the chemical formula. It is close to that of the GdH[B2O5] diborate studied earlier, but has a different orientation of the monoclinicity axis. In both structures the arrangement of atoms follows the pattern of the orthorhombic pseudosupergroup Cmca, which is most distinctly violated by the displacements of the rare-earth atoms. Their common anionic chain radical consists of diborate groups, namely, BO3 triangles and BO4 tetrahedra, 2[1T + 1Δ]. It is shown that the existence of two varieties that are based on the hypothetical orthorhombic prototype is determined by the pseudosymmetry and the difference between the ionic radii of the elements located at the middle and the end of the rare-earth series. The twinning and poor quality of the crystals are related to the effect of the m pseudoplane of the supergroup and cleavage. The structures of natural megaborates that contain diborate chains in complex boron-oxygen radicals are discussed.