A new stacking variant of sodium hexa-hydroxo platinate(IV), Na2Pt(OH)6, was synthesized and its structure elucidated through X-ray diffraction. The new polymorph was prepared by direct reaction of PtO2 with an excess of NaOH solution applying elevated oxygen pressure at 300°C. The structure consists of layers of edge sharing Pt(OH)6 and Na(OH)6 octahedra. These layers are separated by an edge-to-edge distance of ~2.4 Å. The packing of the hydroxide ions corresponds to the hcp sequence, the title compound thus may be regarded a cation ordered variant of the Brucite structure type. During heating above T~300°C all constitutional water is released, and anhydrous Na2PtO3 remains as the solid residue.
Dedicated to: Professor Bernt Krebs on the occasion of his 80th birthday.
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