title: Variable-temperature X-ray diffraction study of structural parameters of NH---S hydrogen bonds in triethylammonium and pyridinium silanethiolates.
abstract: Two hydrogen-bonded, well defined compounds were synthesized from tris(2,6-diisopropyl)phenoxysilanethiol (TDST) and triethylamine (TDST-TEA) or pyridine (TDST-py). The crystalline compounds were characterized in the solid state by variable-temperature X-ray diffraction measurements and ATR FT-IR spectroscopy. The toluene solutions of TDST-TEA and TDST-py were studied by NMR spectroscopy. The total hydrogen-bond energies and FT-IR spectra were calculated with the use of BLYP-D/TZP and B3LYP/6-31G(d,p)/GD3BJ methods. Thermochemical parameters and potential energy scans were calculated at the B3LYP/6-31G(d,p)/GD3BJ level. All results point to the higher energy of bonding in TDST-TEA both in the solid state and in solution. At the same time the potential energy scan reveals a very broad double-well hydrogen bond in TDST-py, indicating good stabilization of the system for a wide range of D-H...A distances.
authors.affiliation: Department of Inorganic Chemistry, Chemical Faculty, Gdańsk University of Technology, Narutowicza 11/12, Gdańsk 80-233, Poland.
authors.forename: Agnieszka
authors.initials: A
authors.lastname: Mielcarek
authors.affiliation: Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2, PO Box 1410, Wrocław 50-950, Poland.
authors.forename: Marek
authors.initials: M
authors.lastname: Daszkiewicz
authors.affiliation: Department of Inorganic Chemistry, Chemical Faculty, Gdańsk University of Technology, Narutowicza 11/12, Gdańsk 80-233, Poland.
authors.forename: Katarzyna
authors.initials: K
authors.lastname: Kazimierczuk
authors.affiliation: Department of Inorganic Chemistry, Chemical Faculty, Gdańsk University of Technology, Narutowicza 11/12, Gdańsk 80-233, Poland.
authors.forename: Anna
authors.initials: A
authors.lastname: Ciborska
authors.affiliation: Department of Inorganic Chemistry, Chemical Faculty, Gdańsk University of Technology, Narutowicza 11/12, Gdańsk 80-233, Poland.
authors.forename: Anna
authors.initials: A
authors.lastname: Dołęga
keywords: DFT calculations; FT–IR spectroscopy; N+—H...S- hydrogen bond; X-ray diffraction