Structure of the Solvated Strontium and Barium Ions in Aqueous, Dimethyl Sulfoxide and Pyridine Solution, and Crystal Structure of Strontium and Barium Hydroxide Octahydrate

Abstract

Single crystal X-ray data, collected at 298 K, are used to redetermine the crystal structure of the non-isomorphic compounds [Sr(H2O)8](OH)2 and [Ba(H2O)8](OH)2. The eight water oxygen atoms form distorted Archimedean antiprisms around the octahydrated metal ions with mean metal ion-oxygen distances 2.62 and 2.79 Å for strontium and barium, respectively. A second coordination shell of 24 hydrogen-bonded oxygen atoms with mean metal ion-oxygen distances M…OII 4.76 and 4.80 Å, respectively, is observed. The hydroxide ions in both structures have an unusual hydrogen bond arrangement with 5 bonds accepted and one donated. The structure of the solvated strontium and barium ions in aqueous, dimethyl sulfoxide and pyridine solutions has been studied by means of large angle X-ray scattering and extended X-ray absorption fine structure spectroscopy techniques. In aqueous solution independent determinations of the first-sphere metal-oxygen coordination by the two techniques resulted in the bond lengths Sr-O 2.63 (2) and Ba-O 2.81 (3) Å, and for both metal ions a hydration number of 8.1 (3). The second coordination spheres are very diffuse with only about 13 water molecules at similar M…OII distances as in the crystal structures and 2-3 water molecules closer to the metal ions. In dimethyl sulfoxide solution both ions were found to coordinate 6.0 (5) solvent molecules with the distances Sr-O 2.54(1), Sr…S 3.77(1) Å, and Ba-O 2.76(1), Ba…S 3.99(1) Å. For the solvated ions in pyridine solution EXAFS measurements yielded the distances Sr-N 2.57 (2) and Ba-N 2.78 (3) Å, with a probable solvation number of 6. Correlations of hydration enthalpies and partial molar volumes with experimental M-O bond distances in aqueous solution are used to discuss hydration numbers and bond character for all of the alkaline earth metal ions.