Expansion of Antimonato\nPolyoxovanadates with Transition\nMetal Complexes: (Co(N<sub>3</sub>C<sub>5</sub>H<sub>15</sub>)<sub>2</sub>)<sub>2</sub>[{Co(N<sub>3</sub>C<sub>5</sub>H<sub>15</sub>)<sub>2</sub>}V<sub>15</sub>Sb<sub>6</sub>O<sub>42</sub>(H<sub>2</sub>O)]·5H<sub>2</sub>O and (Ni(N<sub>3</sub>C<sub>5</sub>H<sub>15</sub>)<sub>2</sub>)<sub>2</sub>[{Ni(N<sub>3</sub>C<sub>5</sub>H<sub>15</sub>)<sub>2</sub>}V<sub>15</sub>Sb<sub>6</sub>O<sub>42</sub>(H<sub>2</sub>O)]·8H<sub>2</sub>O
Elena Antonova (735784)Christian Näther (1518874)Paul Kögerler (1483366)Wolfgang Bensch (1420612)
Abstract
Two new polyoxovanadates (Co(N<sub>3</sub>C<sub>5</sub>H<sub>15</sub>)<sub>2</sub>)<sub>2</sub>[{Co(N<sub>3</sub>C<sub>5</sub>H<sub>15</sub>)<sub>2</sub>}V<sub>15</sub>Sb<sub>6</sub>O<sub>42</sub>(H<sub>2</sub>O)]·5H<sub>2</sub>O (<b>1</b>) and (Ni(N<sub>3</sub>C<sub>5</sub>H<sub>15</sub>)<sub>2</sub>)<sub>2</sub>[{Ni(N<sub>3</sub>C<sub>5</sub>H<sub>15</sub>)<sub>2</sub>}V<sub>15</sub>Sb<sub>6</sub>O<sub>42</sub>(H<sub>2</sub>O)]·8H<sub>2</sub>O (<b>2</b>) (N<sub>3</sub>C<sub>5</sub>H<sub>15</sub> = <i>N</i>-(2-aminoethyl)-1,3-propanediamine)\nwere synthesized under solvothermal conditions and structurally characterized.\nIn both structures the [V<sub>15</sub>Sb<sub>6</sub>O<sub>42</sub>(H<sub>2</sub>O)]<sup>6–</sup> shell displays the main structural\nmotif, which is strongly related to the {V<sub>18</sub>O<sub>42</sub>} archetype cluster. Both compounds crystallize in the triclinic\nspace group <i>P</i>1̅ with <i>a</i> = 14.3438(4), <i>b</i> = 16.6471(6), <i>c</i> = 18.9186(6) Å,\nα = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°,\nand <i>V</i> = 4401.4(2) Å<sup>3</sup> (<b>1</b>) and <i>a</i> = 14.5697(13), <i>b</i> = 15.8523(16), <i>c</i> = 20.2411(18) Å, α = 86.702(11)°, β\n= 84.957(11)°, γ = 76.941(11)°, and <i>V</i> = 4533.0(7) Å<sup>3</sup> (<b>2</b>). In the structure\nof <b>1</b> the [V<sub>15</sub>Sb<sub>6</sub>O<sub>42</sub>(H<sub>2</sub>O)]<sup>6–</sup> cluster anion is bound to a [Co(N<sub>3</sub>C<sub>5</sub>H<sub>15</sub>)<sub>2</sub>]<sup>2+</sup> complex\nvia a terminal oxygen atom. In the Co<sup>2+</sup>-centered complex,\none of the amine ligands coordinates in tridentate mode and the second\none in bidentate mode to form a strongly distorted CoN<sub>5</sub>O octahedron. Similarly, in compound <b>2</b> an analogous\nNiN<sub>5</sub>O complex is joined to the [V<sub>15</sub>Sb<sub>6</sub>O<sub>42</sub>(H<sub>2</sub>O)]<sup>6–</sup> anion via the\nsame attachment mode. A remarkable difference between the two compounds\nis the orientation of the noncoordinated propylamine group leading\nto intermolecular Sb···O contacts in <b>1</b> and to Sb···N interactions in <b>2</b>. In\nthe solid-state lattices of <b>1</b> and <b>2</b>, two\nadditional [M(N<sub>3</sub>C<sub>5</sub>H<sub>15</sub>)<sub>2</sub>]<sup>2+</sup> complexes act as countercations and are located between\nthe [{M(N<sub>3</sub>C<sub>5</sub>H<sub>15</sub>)<sub>2</sub>}V<sub>15</sub>Sb<sub>6</sub>O<sub>42</sub>(H<sub>2</sub>O)]<sup>4–</sup> anions. Between the anions and cations strong N–H···O\nhydrogen bonds are observed. In both compounds the clusters are stacked\nalong the <i>b</i> axis in an ABAB fashion with cations\nand water molecules occupying the space between the clusters. Magnetic\ncharacterization demonstrates that the Ni<sup>2+</sup> and Co<sup>2+</sup> cations do not significantly couple with the <i>S</i> = 1/2 vanadyl groups. The susceptibility data can be successfully\nreproduced assuming a distorted ligand field for the Co<sup>2+</sup> ions (<b>1</b>) and an <i>O</i><sub><i>h</i></sub>-symmetric Ni<sup>2+</sup> ligand field (<b>2</b>).
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