Characterizing the Interactions of Dimethyl Sulfoxide with Water: A Rotational Spectroscopy Study

[Image: see text] The interaction of dimethyl sulfoxide with water has been investigated by Fourier-transform microwave spectroscopy of the 1:1 complex and its isotopologues, complemented with quantum chemical calculations. The rotational spectra of (34)S and (13)C isotopologues in natural abundance and the H(2)(18)O and deuterated water enriched isotopologues have been measured, allowing a partial structure determination and establishing the position of water in the complex. In the most stable conformation water was found to be the donor of a primary OH···OS bond to the oxygen atom of dimethyl sulfoxide and acceptor of two weak CH···OH bonds with the methyl hydrogen atoms of dimethyl sulfoxide. From the structural determination confirmed by quantum chemical calculations, the water molecule lies in the symmetry plane of dimethyl sulfoxide, and the complex has an overall C(s) symmetry. The experimental findings are supported by atoms in molecules and symmetry-adapted perturbation theories, which allowed for determining the hydrogen bond and intermolecular interaction energies, respectively.