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

Abstract

The first lanthanide sulfite compound with a secondary ligand, Nd(SO 3 )(C 2 H 3 O 2 ), was hydrothermally synthesized and solved with single-crystal X-ray diffraction. In order to prevent the facile oxidation of the sulfite to sulfate, careful control of both pH and reaction temperature were required for successful synthesis of the title compound; even slight changes in conditions allow for the facile * Prof. Dr. E. M. Villa E-Mail: EricVilla@Creighton.edu [a]

Syntheses and Structures of the First Lanthanide–Thiosulfate Complexes and the Subsequent Formation of Mixed Thiosulfate–Sulfite Compounds

“…The average S–O bond length in the sulfite anion is 1.534(3) Å. This compares well with the 1.536 Å distance that we have observed in other lanthanide sulfite compounds; , moreover, this structure is very similar to that of a recently reported neodymium mixed sulfite–sulfate structure, Nd­(SO 3 )­(HSO 4 )­(H 2 O) 2 ·(H 2 O) (Figure ). …”

“…It seems quite reasonable to assume that the dissociation of thiosulfate is able to occur at room temperature and, even if this reaction takes place to a minor extent, the decrease in solution dielectric constant from the solvent layering simply encourages the more insoluble phase containing sulfite to precipitate. As has been previously observed, the lanthanide sulfite complexes are known to be quite insoluble. ,, …”

“…13,67,68 When one looks at the bonding within this series (from La to Nd) of mixed thiosulfate−sulfite compounds (using both the potassium and ammonium salts) the average Ln−O bond distance ranges from 2.584(3) Å for the potassium salt of 3) Å. This compares well with the 1.536 Å distance that we have observed in other lanthanide sulfite compounds; 67,68 moreover, this structure is very similar to that of a recently reported neodymium mixed sulfite−sulfate structure, Nd- 3). 67 The final structure type was created through a lowtemperature reaction.…”