Cyclo-S2N2-verbrückte Chlorthionitrenkomplexe von Molybdän und Wolfram. Die Kristallstruktur von μ-(S2N2)[MoCl4(NSCl)]2

Cyclo-S₂N₂ Bridged Chlorothionitrene Complexes of Molybdenum and Tungsten. Crystal Structure of μ-(S₂N₂)MoCl₄(NSCl)]₂ Molybdenum pentachloride reacts with (NSCl)₃ in CH₂Cl₂ suspension giving a product mixture from which the complex μ-(S₂N₂)MoCl₄(NSCl)]₂ can be extracted with CH₂Cl₂. It forms black crystals, whereas the corresponding tungsten compound forms copper-red crystals. μ-(S₂N₂)WCl₄(NSCl)]₂ is obtained by abstraction of SCl₂ and chlorine from N(SCl)₂WCl₅(NSCl)], which can be obtained from WCl₆ and N₂S₃Cl₂. According to their i.r. spectra both complexes μ-(S₂N₂)MCl₄(NSCl)]₂ have the same molecular structure. The crystal structure of μ-(S₂N₂)MoCl₄(NSCl)]₂ was determined and refined with X-ray diffraction data (1851 reflexions, R = 0.019). It crystallizes in the triclinic space group P1 with two molecules per unit cell. The lattice constants are a = 685, b = 735, c = 963 pm, α = 76.6°, β = 80.9°, γ = 87.0°. μ-(S₂N₂)MoCl₄(NSCl)]₂ forms centrosymmetric molecules in which the Mo atoms of the MoCl₄(NSCl) units are linked via the N atoms of a planar N₂S₂ ring. The Mo atoms have coordination number 6, having the N atom of the chlorothionitrene ligand Mo in trans position to the N atom of the S₂N₂ ring.