Hydrogen Bonding and Molecular Geometry in Isolated Hydrates of 2-Ethylthiazole Characterised by Microwave Spectroscopy.

Abstract

Broadband microwave spectra of the isolated 2-ethylthiazole molecule, and complexes of 2-ethylthiazole⋅⋅⋅H2O and 2-ethylthiazole⋅⋅⋅(H2O)2 have been recorded by probing a gaseous sample containing low concentrations of 2-ethylthiazole and water within a carrier gas undergoing supersonic expansion. The identified conformer of the isolated 2-ethylthiazole molecule and the 2-ethylthiazole sub-unit within each of 2-ethylthiazole⋅⋅⋅H2O and 2-ethylthiazole⋅⋅⋅(H2O)2 have C1 symmetry. The angle that defines rotation of the ethyl group relative to the plane of the thiazole ring, ∠(S-C2-C6-C7), is -98.6(10)° within the isolated 2-ethylthiazole molecule. Analysis of molecular geometries and non-covalent interactions reveals each hydrate complex contains a non-linear primary, N⋅⋅⋅Hb-O, hydrogen bond between an O-H of H2O and the nitrogen atom while the O atom of the water molecule(s) interacts weakly with the ethyl group. The ∠(Hb⋅⋅⋅N-C2) parameter, which defines the position of the H2O molecule relative to the thiazole ring, is found to be significantly greater for 2-ethylthiazole⋅⋅⋅H2O than for thiazole⋅⋅⋅H2O. The distance between the O atoms is determined to be 2.894(21) Å within the dihydrate complex which is shorter than observed within the isolated water dimer. The primary hydrogen bond within 2-ethylthiazole⋅⋅⋅(H2O)2 is shorter and stronger than that in 2-ethylthiazole⋅⋅⋅H2O as a result of cooperative hydrogen bonding effects.