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

Abstract

Two isomers of a complex formed between thiazole and two water molecules, thi »(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, A0, B0, and C0; centrifugal distortion constants, DJ, DJK, d1, and d2; and nuclear quadrupole coupling constants, χaa(N) and [χbb(N) - χcc(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 r0 and rs 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 A0, B0, and C0 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 »(H2O)2. The first of these binds H2O to the nitrogen of thiazole (OH »N), and the second binds the two water molecules (OH »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 »O).