title: First anhydrous gold perchlorato complex: ClO(2)Au(ClO(4))(4). Synthesis and molecular and crystal structure analysis.
abstract: Chlorine trioxide, Cl(2)O(6), reacts with Au metal, AuCl(3), or HAuCl(4).nH(2)O to yield the well-defined chloryl salt, ClO(2)Au(ClO(4))(4). The crystal and molecular structure of ClO(2)Au(ClO(4))(4) was solved by a Rietveld analysis of powder X-ray diffraction data. The salt crystallizes in a monoclinic cell, space group C2/c, with cell parameters a = 15.074(5), b = 5.2944(2), and c = 22.2020(2) A and beta = 128.325(2) degrees. The structure displays discrete ClO(2)(+) ions lying in channels formed by Au(ClO(4))(4)(-) stacks. Au is located in a distorted square planar environment: Au-O = 1.87 and 2.06 A. [ClO(4)] groups are monodentate with ClO(b) = 1.53 and ClO(t) = 1.39 A (mean distances; O(b), oxygen bonded to Au; O(t), free terminal oxygen). A full vibrational study of the Au(ClO(4))(4)(-) anion is supported by DFT calculations.
authors.affiliation: LAMMI, UMR CNRS 5072, Case Courrier 15, Université de Montpellier 2, F-34095 Montpellier Cedex 5, France.
authors.forename: Frédérique
authors.initials: F
authors.lastname: Cunin
authors.forename: Catherine
authors.initials: C
authors.lastname: Deudon
authors.forename: Frédéric
authors.initials: F
authors.lastname: Favier
authors.forename: Bernard
authors.initials: B
authors.lastname: Mula
authors.forename: Jean Louis
authors.initials: JL
authors.lastname: Pascal