Secondary interactions in weakly bound complexes: A highly nonlinear hydrogen bond in thiirane·HCN established by rotational spectroscopy

• Published in: Chemical physics letters Vol. 231; no. 2; pp. 151 - 158
• Main Authors: Cosléou, Jean, Lister, David G., Legon, A.C.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 23.12.1994
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/0009-2614(95)90571-5

The ground-state rotational spectra of two isotopomers, (CH 2) 2 32S·HC 14N and (CH 2) 2 32S·HC 15N, of a complex formed by thiirane with hydrogen cyanide were analysed to give rotational constants, centrifugal distortion constants and 14N-nuclear quadrupole coupling constants. The spectroscopic constants were interpreted in terms of a geometry of the complex characterised by the angle φ = 89.2(9)° made by the S·H internuclear axis with the thiirane heavy atom plane at S and a nonlinearity θ≈43° of the S·H-C hydrogen bond. This large nonlinearity is contrasted with that in (CH 2) 2O·HCN and the difference discussed in terms of a simple model of the hydrogen bond.