Polynuclear Cobalt(II/III) Sulfites: Synthesis, Structure, and Magnetic Properties of the Octanuclear Cluster (NH<sub>4</sub>)<sub>11</sub>(Li⊂[Co<sub>4</sub><sup>II</sup>Co<sub>4</sub><sup>III</sup>(SO<sub>3</sub>)<sub>16</sub>(NH<sub>3</sub>)<sub>8</sub>])·10H<sub>2</sub>O Encapsulating a Lithium Cation
Version 2 2008-06-02, 00:00
Version 1 2008-06-02, 00:00
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posted on 2008-06-02, 00:00 authored by George I. Chilas, Marios Stylianou, Maciej Kubicki, Tiverios Vaimakis, Paul Kögerler, Anastasios D. Keramidas, Themistoklis A. KabanosPartial oxidation of an aqueous solution of Co<sup>II</sup>Cl<sub>2</sub>·6H<sub>2</sub>O with (NH<sub>4</sub>)<sub>6</sub>[Mo<sub>7</sub><sup>VI</sup>O<sub>24</sub>]·4H<sub>2</sub>O in the presence of (NH<sub>4</sub>)<sub>2</sub>SO<sub>3</sub>·H<sub>2</sub>O and LiCl, at pH ≈ 5.3, leads to isolation of the octanuclear cluster (NH<sub>4</sub>)<sub>11</sub>(Li⊂[Co<sub>4</sub><sup>II</sup>Co<sub>4</sub><sup>III</sup>(SO<sub>3</sub>)<sub>16</sub>(NH<sub>3</sub>)<sub>8</sub>]·10H<sub>2</sub>O), <b>1</b>. The structure of the anion of <b>1</b> consists of a central [Co<sub>4</sub><sup>II</sup>], almost ideal square planar unit, and a pair of symmetry-related Co<sup>III</sup> dimers above and below the Co<sub>4</sub><sup>II</sup> plane grafting onto the tetramer by 16 bridging sulfite groups. The [Co<sub>8</sub>(SO<sub>3</sub>)<sub>16</sub>(NH<sub>3</sub>)<sub>8</sub>]<sup>12−</sup> cluster encapsulates a lithium cation which lies at the center of the Co<sub>4</sub><sup>II</sup> square.
