α‐RbO₃, a Low Temperature Polymorph of Rubidium Ozonide

Abstract

Applying the known procedure for synthesis of alkali metal ozonides, just at a lower temperature, has yielded a new polymorph of rubidium ozonide, α‐RbO3 [P21; a = 436.3(2), b = 595.3(3), c = 548.7(3) pm, β = 99.680(7), R = 0.0400, 1184 reflections]. Like previously reported β‐RbO3, the basic structural arrangement of anions and cations corresponds to the CsCl type of structure, however, the mutual orientation of the ozonide ions is different, in as much as one of the two terminal oxygen atoms is pointing to the adjacent bridging oxygen atom, forming a chain running along the b axis.

[NEt3Me][O3], Synthesis, Crystal Growth and Crystal Structure Analysis

“…a) The pronounced difference in the OÀ O bond lengths for α-RbO 3 results from presence of a strong intermolecular OÀ O interaction. [10] In contrast to most of the previously reported ionic ozonides, which adopt packing motifs corresponding to the CsCl or NaCl type of structure, [5] the building units of [NEt 3 Me][O 3 ] arrange in a pattern according to the WC type of structure. This feature is illustrated in Figure 5 (left) and Figure S3 and S4, where the nitrogen atoms of the complex cations are connected by dashed lines.…”

“…a) The pronounced difference in the O−O bond lengths for α‐RbO 3 results from presence of a strong intermolecular O−O interaction [10] …”

Formation of Peroxynitrite, [O−N−O−O]−, via a Cascade of Reactions between Ozonide and Ammonia

“…While the puzzling observation of substantial variations of OÀ O bond lengths and OÀ OÀ O bonding angles has been revealed to be a result of electrostatic crystal field effects [5] or CÀ H•••O hydrogen bonding, [6] both polarising the weakly bonded electrons in the 2b 1 anti-bonding HOMO, the promising synthetic potential of the ozonide anion has remained unexplored, so far. Radical recombination, i. e., dimerization to form (O 6 ) 2À in analogy to the behaviour of the (S 3 ) À radical anion, is among the first options that come to mind.…”