Crystal Structure of Cl₂O₆

Abstract

Cl2O6 is present as ionic chloryl perchlorate, ClO 2⊖ClO 4⊖, in the crystalline state. This is not surprising in view of the chemical behavior of Cl2O6–it is used as perchlorate “supplier” for the synthesis of anhydrous perchlorates–but was not to be expected according to the results of earlier structural investigations. The Cl–O distance in the ClO 2⊕ ion (ca. 141 pm) is much shorter than in the neutral ClO2 in the gas phase. Each cation is coupled with two anions (and conversely) to give polymeric groups.

Reactions of ClF3 with Main Group and Transition Metal Oxides: Access to Dioxychloronium(V) Fluoridometallates and Oxidofluoridometallates

“…Due to the shorter Cl−O bonds in comparison to the much longer Cl ⋅ ⋅ ⋅ μ−F interactions, the Cl atom is displaced from the center of the coordination polyhedron. In comparison to previously reported crystal structures of [ClO 2 ] + compounds, such as [ClO 2 ][BF 4 ], [ClO 2 ][RuF 6 ], [ClO 2 ][SbF 6 ], [ClO 2 ][Sb 2 F 11 ], or [ClO 2 ][ClO 4 ], the coordination number of the Cl atom is unexpectedly high [34,39,41,43,44] . Usually, only four short contacts of O or F atoms from surrounding anions are observed.…”

“…The Cl atom of the [ClO 2 ] + cation is always surrounded by additional bridging ligands, either F atoms in fluoridometallate or oxidofluoridometallate salts or O atoms in perchlorate‐containing compounds [37–40] . The coordination number of the Cl atom in the investigated compounds is usually 2+4, with a distorted octahedral arrangement of the ligands, see Table 9.…”

“…Compounds with [ClO 2 ] + or [BrO 2 ] + ions are furthermore obtained when X O 3 F ( X =Cl, Br) is reacted with strong Lewis acids [34] . In the case of [ClO 2 ] + cations, reactions of Cl 2 O 6 (“[ClO 2 ][ClO 4 ]”) with metals or chlorides often lead to the formation of dioxychloronium(V) perchloratometallates, where [ClO 4 ] − anions are bound as ligands [35–40] . Crystal structures of [ClO 2 ] + salts with the following anions have been reported: [BF 4 ] − , [GeF 2/2 F 4/1 ] − , [RuF 6 ] − , [SbF 6 ] − , [Sb 2 F 11 ] − , [ClO 4 ] − , [Au(ClO 4 ) 4 ] − and [Sn(ClO 4 ) 6 ] 2− [34,37–44] .…”

“…In the case of [ClO 2 ] + cations, reactions of Cl 2 O 6 (“[ClO 2 ][ClO 4 ]”) with metals or chlorides often lead to the formation of dioxychloronium(V) perchloratometallates, where [ClO 4 ] − anions are bound as ligands [35–40] . Crystal structures of [ClO 2 ] + salts with the following anions have been reported: [BF 4 ] − , [GeF 2/2 F 4/1 ] − , [RuF 6 ] − , [SbF 6 ] − , [Sb 2 F 11 ] − , [ClO 4 ] − , [Au(ClO 4 ) 4 ] − and [Sn(ClO 4 ) 6 ] 2− [34,37–44] . Recently, compounds were published containing the complex [Cl 2 BrO 6 ] + cation that might be considered as a central [BrO 2 ] − anion coordinating to two [ClO 2 ] + cations [45] …”

The SAGES manual: fundamentals of laparoscopy, thoracoscopy, and GI endoscopy. 2nd Edn. C. E. H. Scott-Conner (ed.). 127 × 201 mm. Pp 840. Illustrated. 2006. Springer: Heidelberg. £38·50

“…The structural, spectroscopic and chemical properties of ClO 3 and Cl 2 O 6 have remained controversial over nearly 150 years 47, 87–98. Finally, for Cl 2 O 6 , a X‐ray crystallographic analysis of the low temperature solid has confirmed an ionic structure ClO 2 + ClO 4 − ,99, 100 while an IR gas phase and matrix isolation study have suggested a molecular structure of O 2 ClOClO 3 101–103. In the gas phase Cl 2 O 6 decomposes rapidly into OClO and O 2 and is not in equilibrium with the anticipated ClO 3 radicals 103.…”