Abstract: | An Anionic Oxohydroxo Complex with Bismuth(III): Na6[Bi2O2(OH)6](OH)2 · 4H2O Colourless, plate‐like, air sensitive crystals of Na6[Bi2O2(OH)6](OH)2 · 4H2O are obtained by reaction of Bi2O3 or Bi(NO3)3 · 5H2O in conc. NaOH (58 wt %) at 200 °C followed by slow cooling to room temperature. The crystal structure (triclinic, P 1¯, a = 684.0(2), b = 759.8(2), c = 822.7(2) pm, α = 92.45(3)°, ß = 90.40(3)°, γ = 115.60(2)°, Z = 1, R1, wR2 (all data), 0, 042, 0, 076) contains dimeric, anionic complexes [Bi2O2(OH)6]4— with bismuth in an ψ1‐octahedral coordination of two oxo‐ and three hydroxo‐ligands. The thermal decomposition was investigated by DSC/TG or DTA/TG and high temperature X‐ray powder diffraction measurements. In the final of three steps the decomposition product is Na3BiO3. |