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

Abstract The hydrogen bonds involving sulfur in the furfuryl mercaptan monohydrate are compared with the interactions originating from the hydroxyl group in furfuryl alcohol. The dimers with water were created in a supersonic jet expansion and characterized using microwave spectroscopy and supporting molecular orbital calculations. In furfuryl alcohol–water, a single isomer is observed, in which the water molecule forms an insertion complex with two simultaneous hydrogen bonds to the alcohol (O−H⋅⋅⋅O w ) and the ring oxygen (O w −H⋅⋅⋅O r ). When the alcohol is replaced by a thiol group in furfuryl mercaptan–water, two isomers are observed, with the thiol group preferentially behaving as proton donor to water. The first isomer is topologically equivalent to the alcohol analog but the stronger hydrogen bond is now established by water and the ring oxygen, assisted by a thiol S−H⋅⋅⋅O w hydrogen bond. In the second isomer the sulfur group accepts a proton from water, forming a O w −H⋅⋅⋅S hydrogen bond. Binding energies for the mercaptan–water dimer are predicted around 12 kJ mol −1 weaker than in the alcohol hydrate (B3LYP‐D3(BJ)). The non‐covalent interactions in the furfuryl dimers are dominantly electrostatic according to a SAPT(0) energy decomposition, but with increasing dispersion components in the mercaptan dimers, which are larger for the isomer with the weaker O w −H⋅⋅⋅S interaction.