Synthesen und Kristallstrukturen von PPh4[RuCl4(NO)(NSCl)] und (PPh4)2[RuCl4(NS)]2·4C H2Cl2 / Syntheses and Crystal Structures of PPh4[RuCl4(NO)(NSCl)] and (PPh4)2[RuCl4(NS)]2·4C H2Cl2

Abstract

Abstract By reaction of trithiazylchloride, (NSCl)3, with PPh4[RuCl4(NO)]2 in dichloromethane the thiazylchloridenitrosyl complex PPh4[RuCl4(NO)(NSCl)] is obtained; its vacuum pyrolysis at 200-220 °C yields the thionitrosyl com plex (PPh4)2[RuCl4(NS)]2 which crystallizes from CH2Cl2 solution with four molecules of CH2Cl2. Both com pounds were charaterized by their IR spectra and by X-ray crystal structure determinations. Crystal data: PPh4[RuCl4(NO)(NSCl)], mono­clinic, space group P 21/n, Z = 4, a = 982.6, b = 1700.0, c = 1772.3 pm , β = 104.79° (2548 observed reflexions, R = 0.046); (PPh4)2[RuCl4(NS)]2·4CH2Cl2, triclinic, P1̄ , Z = 1, a = 952.9, b = 1380.0, c = 1458.5 pm , α = 112.91, β = 106.67, γ = 92.61° (3760 observed reflexions, R = 0.053). In the [RuCl4(NO)(NSCl)]⊖ ion the nitrosyl and thiazyl chloride ligands occupy ex ­ positions; bond lengths indicate double bonds in the linear Ru=N=O group, while the NSCl molecule is attached by a donor-acceptor interaction Ru-N≡S̲-Cl , although with a rather short Ru-N bond of 198 pm (N≡S 144 pm, S-Cl 213 pm). The centrosymmetric [RuCl4(NS)]2 2⊖ ions have chloro bridges and NS ligands in axial positions; the nearly linear Ru=N=S group has bond lengths Ru=N 175 pm and N=S 147 pm.