Zirconium Oxalates: Zr(OH)<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>), (H<sub>11</sub>O<sub>5</sub>)<sub>2</sub>[Zr<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>5</sub>(H<sub>2</sub>O)<sub>4</sub>], and MM′[Zr(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]·<i>x</i>H<sub>2</sub>O with M and M′ = Ammonium,\nAlkali Metal, and Hydroxonium Ion H<sub>2<i>n</i>+1</sub>O<sub><i>n</i></sub><sup>+</sup> (<i>n</i> =\n2, 3, 4)
Rudy Thomas (9243529)Philippe Devaux (6640184)Murielle Rivenet (1444222)Natacha Henry (1434346)Francis Abraham (1444210)
Abstract
Crystallized\npowder of dihydroxide zirconium oxalate Zr(OH)<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>) (<b>ZrOx</b>) was obtained\nby precipitation and the structure determined from powder X-ray data.\nThe three-dimensional (3D) framework observed in (<b>ZrOx</b>) results from the interconnection of zirconium hydroxide chains <sup>1</sup><sub>∞</sub>[Zr(OH)<sub>2</sub>]<sup>2+</sup> and zirconium\noxalate chains <sup>1</sup><sub>∞</sub>[{Zr(C<sub>2</sub>O<sub>4</sub>)}<sup>2+</sup>]. Single crystals of (H<sub>11</sub>O<sub>5</sub>)<sub>2</sub>[Zr<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>5</sub>(H<sub>2</sub>O)<sub>4</sub>] (<b>H2Zr2O5</b>) were\nobtained by evaporation. The structure contains dimeric anions [Zr<sub>2</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>5</sub>(H<sub>2</sub>O)<sub>4</sub>]<sup>2–</sup> connected through hydrogen bonds to\nhydroxonium ions (H<sub>11</sub>O<sub>5</sub>)<sup>+</sup> to create\na 3D supramolecular framework. The addition of ammonium or alkali\nnitrate led to the formation of single crystals of Na<sub>2</sub>[Zr(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]·2H<sub>2</sub>O (<b>Na2ZrOx3</b>), M(H<sub>7</sub>O<sub>3</sub>)[Zr(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]·H<sub>2</sub>O, M = K (<b>KHZrOx3</b>), M = NH<sub>4</sub> (<b>NH4HZrOx3</b>), M(H<sub>5</sub>O<sub>2</sub>)<sub>0.5</sub>(H<sub>9</sub>O<sub>4</sub>)<sub>0.5</sub>[Zr(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>], M = Rb (<b>RbHZrOx3</b>), and\nM = Cs (<b>CsHZrOx3</b>). For the five compounds, the structure\ncontains ribbons <sup>1</sup><sub>∞</sub>[{ZrOx<sub>3</sub>}<sup>2–</sup>] formed by entities Zr(C<sub>2</sub>O<sub>4</sub>)<sub>4</sub> sharing two oxalates. In (<b>Na2ZrOx3</b>), the\nshared oxalates are in cis positions and the chain <sup>1</sup><sub>∞</sub>[Zr–Ox] is stepped with a Zr–Zr–Zr\nangle of 98.27(1)°. In the other compounds, the shared oxalates\nare in trans positions and the chains <sup>1</sup><sub>∞</sub>[Zr–Ox] are corrugated with Zr–Zr–Zr angles\nin the range 140.34(1)–141.07(1)°. In the compounds (<b>MHZrOx3</b>), the cohesion between the ribbons is ensured by the\nalkaline or ammonium cations and the hydroxonium ions (H<sub>7</sub>O<sub>3</sub>)<sup>+</sup> for M = K, NH<sub>4</sub>, (H<sub>5</sub>O<sub>2</sub>)<sup>+</sup>, and (H<sub>9</sub>O<sub>4</sub>)<sup>+</sup> for M = Rb and Cs. During the thermal decomposition of the\nalkaline-free zirconium oxalates (<b>ZrOx</b>), (<b>H2Zr2Ox5</b>), and (<b>NH4HZrOx3</b>), the formed amorphous zirconia is\naccompanied by carbon; the oxidation of carbon at about 540 °C\nto carbon dioxide is concomitant with the crystallization of the stabilized\ntetragonal zirconia.
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