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Synthesis, Crystal Structure, and Spectroscopic Characterization of Na 5 [NiO 2 ][CO 3 ], containing the Linear [NiO 2 ] 3– Group with Monovalent Nickel
Author(s) -
Möller Angela
Publication year - 2001
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/1521-3749(200112)627:12<2625::aid-zaac2625>3.0.co;2-k
Subject(s) - tetragonal crystal system , chemistry , crystal structure , crystallography , nickel , metal , transition metal , inorganic chemistry , catalysis , biochemistry , organic chemistry
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.