Blo¨dite-type compounds Na2Me(SO4)2·4H2O (Me ¼ Mg, Co, Ni, Zn): crystal structures and hydrogen bonding systems

The crystal structures of synthetic blo¨dite-type compounds Na2Me2þ(SO4)2·4H2O (Me ¼ Mg, Co, Ni, Zn) were investigated using single crystal X-ray CCD diffraction data. They crystallize isotypic (space group P21/a) and are built up from [Me(H2O)4(SO4)2]22 clusters which are interlinked by NaO6 polyhedra and hydrogen bonds of medium strength. While the octahedral mean Me–O bond lengths follow the trends expected from the cationic radii (Ni , Mg , Zn # Co), several other structural features do not, e.g. the cell volumes (Ni , Zn , Co # Mg) or the ‘cluster angles’ Me–O–S. Such deviations are attributed to a slightly different bonding character of the Mg–O bond compared to the 3d transition ions. The strengths of the hydrogen bonds formed in the title compounds as deduced from the infrared wavenumbers of the respective uncoupled OD stretching modes of matrix-isolated HDO molecules (isotopically dilute samples) are discussed in terms of hydrogen bond lengths Ow· · ·O and metal–water interactions (synergetic effect). The red-shift of the bands corresponding to the OD stretches on going from the magnesium to the zinc compound is caused by the increasing covalency of the respective Me–OH2 bonds (Mg , Co , Ni , Zn). The intramolecular OH bond distances are derived from the novel nOD vs. rOH correlation curves [J. Mol. Struct. 351 (1995) 205; J. Mol. Struct. 404 (1997) 63]. q 2004 Elsevier B.V. All rights reserved