The Carbonyl-Sulfur Chalcogen Bonding Interaction: Rotational Spectroscopic Study of the 2,2,4,4-Tetrafluoro-1,3-dithietane···formaldehyde Complex

The rotational spectrum of a binary molecular cluster consisting of 2,2,4,4-tetrafluoro-1,3-dithietane (C2S2F4) and formaldehyde (H2CO) was studied by means of high-resolution Fourier transform microwave spectroscopy in conjunction with quantum chemical calculations. One of the three isomers predicted at the B3LYP-D3(BJ)/def2-TZVP level of theory was successfully detected in the supersonic expansion. Theoretical analyses using the non-covalent interactions and natural bond orbital methods reveal that the observed isomer is primarily stabilized by one C=O⋯S chalcogen bond and two C−H⋯F hydrogen bonds. The distance between the oxygen atom of H2CO and the nearest sulfur atom of C2S2F4 within the observed isomer is 2.9260(1) Å and the angle ∠O⋯S−C is 161.83(1)°. The analysis utilizing the symmetry-adapted perturbation theory approach demonstrates that electrostatic interactions play a significant role in stabilizing the studied complex, with the contribution of dispersion interactions being comparable to that of electrostatic ones