Synthesis, Crystal Structure, and Spectroscopic Characterization of Na5[NiO2][CO3], containing the Linear [NiO2]3– Group with Monovalent Nickel

✍ Scribed by Angela Möller

• Publisher: John Wiley and Sons
• Year: 2001
• Tongue: German
• Weight: 116 KB
• Volume: 627
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/1521-3749(200112)627:12<2625::aid-zaac2625>3.0.co;2-k

✦ Synopsis

For the first time ruby-red single crystals and powder samples of Na 5 [NiO 2 ][CO 3 ] were obtained via a redox reaction between nickel metal and CdO in the presence of Na 2 O and Na 2 CO 3 (molar ratios of CdO : Na 2 O : Na 2 CO 3 equal 1 : 3 : 2). The crystal structure has been refined from single crystal X-ray diffraction data at 170 K (tetragonal, P4/ mmm, a = 462.7(1) pm, c = 830.5(2) pm) and at 293 K (a = 462.35(7) pm, c = 830.9(1) pm). Na 5 [NiO 2 ][CO 3 ] is the first example of an alkaline-rich transition metal oxide with two different oxoanions, [NiO 2 ] 3± and [CO 3 ] 2± , coexisting in one compound. The electronic spectrum of Na 5 [NiO 2 ][CO 3 ] has been measured between 4000 and 25000 cm ±1 . Two d-d-transitions of the linear [NiO 2 ] 3± complex (d 9 ) are observed at 5870 cm ±1 and 11850 cm ±1 and analysed using the angular overlap model. MIR and FIR spectra give evidence for the [CO 3 ] 2± anion present in the structure.