Dy₂(SO₃)₂(SO₄)(H₂O)₂: the first lanthanide mixed sulfate–sulfite inorganic compound

Abstract

The first lanthanide mixed sulfate-sulfite inorganic coordination polymer, poly[diaqua-μ(4)-sulfato-di-μ(4)-sulfito-didysprosium(III)], [Dy(2)(SO(3))(2)(SO(4))(H(2)O)(2)](n), has been obtained, in which both sulfate and sulfite groups originate from the disproportionation of S(2)O(3)(2-) under hydrothermal and weakly acidic conditions. The crystal structure of the title compound exhibits a three-dimensional framework. The Dy(III) ion is surrounded by eight O atoms from one water molecule and two sulfate and five sulfite groups. These DyO(8) polyhedra have two shared edges and form an infinite zigzag Dy-O chain. In the bc plane, neighbouring chains are integrated through SO(3) trigonal pyramids, forming a two-dimensional sheet. Along the a-axial direction, the sulfate group, with the central S atom lying on a twofold axis, links adjacent two-dimensional sheets via two S-O-Dy connections, thus generating the three-dimensional framework.

pH Driven Hydrothermal Syntheses of Neodymium Sulfites and Mixed Sulfate-Sulfites

“…These structure types have applications in piezoelectricity, pyroelectricity, and second-harmonic generation. − It is in this vein that we seek to examine the synthesis of single-crystal lanthanide sulfites. Lanthanide sulfites are largely unexplored in the literature mainly because of their low solubility, but some preliminary studies have been done on their properties. − The reaction of lanthanide cations and the sulfite anion yields an insoluble product that will not completely dissolve in aqueous solution at room temperature. To date, only three of lanthanide sulfite structures have been elucidated from single-crystal or powder diffraction data, and none of them have produced a pure lanthanide sulfite via hydrothermal synthesis. ,− Herein, we discuss the syntheses and structures of four new neodymium sulfite and mixed sulfite-hydrogen-sulfate structures.…”

“…29−31 It is in this vein that we seek to examine the synthesis of single-crystal lanthanide sulfites. Lanthanide sulfites are largely unexplored in the literature mainly because of their low solubility, 32 but some preliminary studies have been done on their properties. 33−38 The reaction of lanthanide cations and the sulfite anion yields an insoluble product that will not completely dissolve in aqueous solution at room temperature.…”

Synthesis, Characterization, and Structural Comparisons of the First Neodymium(III) Sulfite‐Acetate Crystal Structure

“…Recently, we have endeavored to explore the formation of new lanthanide compounds via in‐situ ligand redox reactions. The first system studied was a lanthanide sulfite system, from which we were able to isolate four new neodymium sulfite and mixed sulfate‐sulfite compounds, building off of previous lanthanide sulfite works . The sulfite anion (SO 3 2– ) has C 3 v symmetry and a stereoactive lone pair; it is also easily oxidized to sulfate under aerobic conditions.…”