Cooperative hydrogen bonding in thiazole???(H₂O)₂ revealed by microwave spectroscopy

Two isomers of a complex formed between thiazole and two water molecules, thi center dot center dot center dot(H2O)(2), have been identified through Fourier transform microwave spectroscopy between 7.0 and 18.5 GHz. The complex was generated by the co-expansion of a gas sample containing trace amounts of thiazole and water in an inert buffer gas. For each isomer, rotational constants, A(0), B-0, and C-0; centrifugal distortion constants, D-J, D-JK, d(1), and d(2); and nuclear quadrupole coupling constants, ?(aa)(N) and [?(bb)(N) - ?(cc)(N)], have been determined through fitting of a rotational Hamiltonian to the frequencies of observed transitions. The molecular geometry, energy, and components of the dipole moment of each isomer have been calculated using Density Functional Theory (DFT). The experimental results for four isotopologues of isomer I allow for accurate determinations of atomic coordinates of oxygen atoms by r(0) and r(s) methods. Isomer II has been assigned as the carrier of an observed spectrum on the basis of very good agreement between DFT-calculated results and a set of spectroscopic parameters (including A(0), B-0, and C-0 rotational constants) determined by fitting to measured transition frequencies. Non-covalent interaction and natural bond orbital analyses reveal that two strong hydrogen bonding interactions are present within each of the identified isomers of thi center dot center dot center dot(H2O)(2). The first of these binds H2O to the nitrogen of thiazole (OH center dot center dot center dot N), and the second binds the two water molecules (OH center dot center dot center dot O). A third, weaker interaction binds the H2O sub-unit to the hydrogen atom that is attached to C2 (for isomer I) or C4 (for isomer II) of the thiazole ring (CH center dot center dot center dot O). (C) 2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).