Reaction of Pertechnetate in Highly Alkaline Solution: Synthesis and Characterization of the Nitridotrioxotechnetate Ba[TcO(3)N]

The preparation of novel technetium oxides, their characterization and the general investigation of technetium chemistry are of significant importance, since fundamental research has so far mainly focused on the group homologues. Whereas the structure chemistry of technetium in strongly oxidizing media is dominated by the [Formula: see text] anion, our recent investigation yielded the new [Formula: see text] anion. Brown single crystals of Ba[TcO(3)N] were obtained under hydrothermal conditions starting from Ba(OH)(2) ⋅ 8H(2)O and NH(4)[TcO(4)] at 200 °C. [Formula: see text] crystallizes in the monoclinic crystal system with the space group P2(1)/n (a=7.2159(4) Å, b=7.8536(5) Å, c=7.4931(4) Å and β=104.279(2)°). The crystal structure of [Formula: see text] consists of isolated [Formula: see text] tetrahedra, which are surrounded by Ba(2+) cations. XANES measurements complement the oxidation state +VII for technetium and Raman spectroscopic experiments on Ba[TcO(3)N] single crystals exhibit characteristic Tc−O and Tc−N vibrational modes.