Reactivity, Syntheses, and Crystal Structures of Na5[MO2][X] with M = Co+, Ni+, Cu+; X = CO32—, SO42—, SO32—, S2—, and Na25[CuO2]5[SO4]4[S

Abstract

AbstractNa5[CuO2][CO3], Na5[CuO2][SO3], Na5[CuO2][S], and Na5[CuO2][SO4] were obtained as single crystals and powders from reactions of Na2O, Cu2O, and Na2X with X = CO32—, SO32—, S2—, and SO42—, respectively. A redox reaction between CdO and Co metal occurs in the presence of Na2O and Na2X, yielding Na5[CoO2][X] with X = CO32— and S2—. From a mixture of Na2SO4, CdO and Na2O in Ni‐containers we observed the formation of Na5[NiO2][S] single crystals. Single crystals of Na25[CuO2]5[SO4]4[S] can be grown by annealing Na5[CuO2][SO3] at 600 °C, leading to the decomposition of SO32—, yielding SO42— and S2— at 550 °C. The structures have been determined from single crystal data and powder data. All structures contain the isolated complex [MO2]3— in a dumb‐bell like arrangement. The main feature of these compounds is that the anions SO42—, SO32—, CO32— and S2— are not connected to the transition metal. The formation of Na5[CuO2][X] (X = S2—, SO42—, SO32—, CO32—) has been studied by thermal analysis and in situ X‐ray diffraction techniques. Infrared spectra confirm the presence of SO42—, SO32—, and CO32—, respectively, in the structures.