PREPARATION, CHARACTERIZATION, AND CRYSTAL-STRUCTURE OF [CLO2]+[RUF6]- - CRYSTAL-STRUCTURE OF [CLF2]+[RUF6]-

Chloryl hexafluororuthenate(V), [ClO2]+[RuF6]-, is prepared either by fluorination of RuO4 using ClF3 in HF solution at room temperature or by the reaction of ClO2F with RuF5. This salt, which like its counterpart [ClF2]+[RuF6]- is a powerful oxidizer, is characterized by elemental analysis, X-ray powder data, and vibrational spectroscopy. The crystal structure of this salt shows that the ruthenium atom, located on a C-2 axis, is surrounded by a weakly distorted octahedron of fluorine atoms with six comparable bond lengths. The space group, unit cell parameters, and R factor are as follows: P2/n (No. 13), a = 7.187 (6) angstrom, b = 5.653 (3) angstrom, c = 7.260 (5) angstrom, beta = 90.87 (6)-degrees, V = 294.9 (6) angstrom-3, Z = 2, R = 0.055. The structure of difluorochlorine(III) hexafluororuthenate(V), [ClF2]+[RuF6]-, obtained from the reaction of an excess of ClF3 with RuF5, is also reported and its characteristics are compared with those of [ClO2]+[RuF6]-. The space group, unit cell parameters, and R factor of [ClF2]+[RuF6]- are as follows: orthorhombic, Pcca (No. 54), a = 19.957 (4) angstrom, b = 5.649 (2) angstrom, c = 10.616 (6) angstrom, V = 1197 (1) angstrom-3, Z = 8, R = 0.038. The vibrational spectra of both salts are discussed in light of the structures determined.