Osmium pentafluoride, structure

It has been suggested (79) that polymorphism may occur for transition metal pentafluorides as it does for oxide tetrafluorides (91). X-Ray powder photographs of products from the reduction of hexafluorides in anhydrous hydrogen fluoride (79) showed that the samples of rhenium and osmium pentafluorides had different structures from those previously reported, but no unit-cell dimensions could be derived. 

Although the third structure type was established for ruthenium pentafluoride (88), the results were based on restricted single-crystal data, giving less accurate molecular dimensions. Full data were used for the structure analysis of the osmium compound (89 ) but the results were still unsatisfactory, because of the predominant scattering by the... 

Although a number of complex fluorides of quinquevalent iridium, (e.g. KIrF,) are known, previous attempts to establish the simple fluoride have failed. The absence of a pentafluoride of iridium has become increasingly anomalous as the pentafluorides of the neighbouring elements, rhenium, osmium, and platinum have been prepared. Previous work - indicated that reactions which might have yielded the pentafluoride gave the tetrafluoride instead. The physical properties of this tetrafluoride. (m.p. 106—107 b.p. > 300 ), however, resembled those of a pentafluoride or oxide tetrafluoride. This indicated that iridium tetrafluoride differed structurally from its neighbouring tetrafluorides. 

Rhodium pentafluoride is isomorphous with its ruthenium, osmium, and iridium analogues, the crystal data being a, 12-28 b, 9-86 c, 6-48 A ]3, 99-2° Uobs-, 654-2 A Z = 8. Presumably the structural unit of this compound is a fluorine-bridged tetramer, as in ruthenium pentafluoride. It is noteworthy that the unit-cell volume is smaller than in the ruthenium analogue, possibly as a... 

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