Monoprotonated Dimethyl Sulfoxide, [HOSMe ₂ ] ⁺ : Synthesis, Crystal Structure, Spectroscopic and Theoretical Studies of [HOSMe ₂ ] ₂ [OsCl ₆ ] ⋅ 2H ₂ O

Complex [H(dmso)] 2 [Os IV Cl 6 ] ⋅ 2H 2 O ( 1 ) was synthesized by refluxing of [H(dmso) 2 ] 2 [OsCl 6 ] 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 [Me 2 S=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.