Monoprotonated Dimethyl Sulfoxide, [HOSMe2]+: Synthesis, Crystal Structure, Spectroscopic and Theoretical Studies of [HOSMe2]2[OsCl6] ⋅ 2H2O

Complex [H(dmso)]2[OsIVCl6] ⋅ 2H2O (1) was synthesized by refluxing of [H(dmso)2]2[OsCl6] in concentrated HCl and characterized by the IR and UV/Vis spectroscopy and X-ray powder and single-crystal diffraction studies. In this complex, rare highly electrophilic [Me2S=O⋅⋅⋅H]+ cation is stabilized by multiple chalcogen bonds including bifurcated S⋅⋅⋅(Cl)3 and S⋅⋅⋅Cl non-covalent interactions. DFT calculations and topological analysis of the electron density distribution within the formalism of Bader's theory (QTAIM method) support the presence of intermolecular non-covalent interactions S⋅⋅⋅Cl and O⋅⋅⋅Cl in the solid state. © 2021 Wiley-VCH GmbH