Conformation and Stability of Adducts of Sulfurated Cyclic Compounds with Water:  Rotational Spectrum of Tetrahydrothiophene−Water

Abstract

The ground-state rotational spectrum of the tetrahydrothiophene···water complex (C4H8S···H2O) has been studied by free jet millimeter wave absorption and molecular beam Fourier transform microwave spectroscopy. The spectra of H2O and D2O combined with C4H8 32S and C4H8 34S were assigned. The rotational parameters have been interpreted in terms of a geometry in which the water molecule acts as proton donor lying close to the plane bisector to the CSC angle of tetrahydrothiophene. The “free” hydrogen is entgegen to the ring. The parameters characterizing the hydrogen bond are the distance between the sulfur and hydrogen atoms, r(S···H) = 2.37(4) Å, and the angle between the line bisecting the CSC angle of tetrahydrothiophene and the S···H bond, φ = 85.(3)°. The deviation from collinearity of the atoms S···H−O is suggested from θ = 162.(12)°.

Sulfur Hydrogen Bonding in Isolated Monohydrates: Furfuryl Mercaptan versus Furfuryl Alcohol

“…When the thiol group behaves as proton acceptor in isomer GG–W dd the water molecule is weakly bound to the sulfur atom ( r (O w H⋅⋅⋅S)=2.95(3) Å), and the water oxygen similarly sits closer to the furfuryl plane ( r (O w H⋅⋅⋅O r )=1.95 Å), as in the furan hydrate. In tetrahydrothiophene–water, the only O w H⋅⋅⋅S hydrogen bond was found much shorter ( r (O w H⋅⋅⋅S)=2.37(4) Å) . For comparison, in the prototype hydrogen sulfide dimer the hydrogen bond distance is r (SH⋅⋅⋅S)=2.779(4) Å .…”

Relative Strengths of the OH⋅⋅⋅Cl and OH⋅⋅⋅F Hydrogen Bonds

“…The structural and energetic features of hydrogen bonding between water and organic molecules were recently investigated in detail by high‐resolution spectroscopic analysis of hydrogen‐bonded complexes 3. The OH⋅⋅⋅O, OH⋅⋅⋅N, OH⋅⋅⋅S, and NH⋅⋅⋅O interactions were characterized through rotational‐spectroscopic studies of molecular complexes of water with ethers,4 amines,5 diazines,6 thioethers,7 and imino groups inserted into aromatic rings;8 all of those represent relatively strong hydrogen bonds, with energies in the range 15–25 kJ mol −1 . The OH⋅⋅⋅F interaction was investigated with this technique as well, through analysis of the rotational spectrum of the complex of freon‐32 (difluoromethane) with water 9.…”

Dynamical Behavior and Dipole–Dipole Interactions of Tetrafluoromethane–Water

“…Hydrogen bonding is the most important of such interactions; it involves many scientific areas and is invoked to explain the energetic and structural features of inorganic, organic, and biological systems 2. Classical hydrogen bonds are OH⋅⋅⋅O,3 OH⋅⋅⋅N,4 OH⋅⋅⋅S,5 and NH⋅⋅⋅O 6. All of these are relatively strong hydrogen bonds with energies in the range 15–25 kJ mol −1 .…”