O-H⋅⋅⋅N and C-H⋅⋅⋅O hydrogen bonds control hydration of pivotal tropane alkaloids: tropinone⋅⋅⋅H(2)O complex. 2014

Patricia Ecija, and Montserrat Vallejo-López, and Luca Evangelisti, and José A Fernández, and Alberto Lesarri, and Walther Caminati, and Emilio J Cocinero
Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV-EHU), Apartado 644, 48940 Bilbao (Spain) http://grupodeespectroscopia.es/MW/

The effect of monohydration in equatorial/axial isomerism of the common motif of tropane alkaloids is investigated in a supersonic expansion by using Fourier-transform microwave spectroscopy. The rotational spectrum reveals the equatorial isomer as the dominant species in the tropinone⋅⋅⋅H2 O complex. The monohydrated complex is stabilized primarily by a moderate OH⋅⋅⋅N hydrogen bond. In addition, two CH⋅⋅⋅O weak hydrogen bonds also support this structure, blocking the water molecule and avoiding any molecular dynamics in the complex. The water molecule acts as proton donor and chooses the ternary amine group over the carbonyl group as a proton acceptor. The experimental work is supported by theoretical calculations; the accuracy of the B3LYP, M06-2X, and MP2 methods is also discussed.

UI MeSH Term Description Entries
D007536 Isomerism The phenomenon whereby certain chemical compounds have structures that are different although the compounds possess the same elemental composition. (From McGraw-Hill Dictionary of Scientific and Technical Terms, 5th ed) Isomerisms
D010100 Oxygen An element with atomic symbol O, atomic number 8, and atomic weight [15.99903; 15.99977]. It is the most abundant element on earth and essential for respiration. Dioxygen,Oxygen-16,Oxygen 16
D002244 Carbon A nonmetallic element with atomic symbol C, atomic number 6, and atomic weight [12.0096; 12.0116]. It may occur as several different allotropes including DIAMOND; CHARCOAL; and GRAPHITE; and as SOOT from incompletely burned fuel. Carbon-12,Vitreous Carbon,Carbon 12,Carbon, Vitreous
D006859 Hydrogen The first chemical element in the periodic table with atomic symbol H, and atomic number 1. Protium (atomic weight 1) is by far the most common hydrogen isotope. Hydrogen also exists as the stable isotope DEUTERIUM (atomic weight 2) and the radioactive isotope TRITIUM (atomic weight 3). Hydrogen forms into a diatomic molecule at room temperature and appears as a highly flammable colorless and odorless gas. Protium,Hydrogen-1
D006860 Hydrogen Bonding A low-energy attractive force between hydrogen and another element. It plays a major role in determining the properties of water, proteins, and other compounds. Hydrogen Bonds,Bond, Hydrogen,Hydrogen Bond
D000470 Alkaloids Organic nitrogenous bases. Many alkaloids of medical importance occur in the animal and vegetable kingdoms, and some have been synthesized. (Grant & Hackh's Chemical Dictionary, 5th ed) Alkaloid,Plant Alkaloid,Plant Alkaloids,Alkaloid, Plant,Alkaloids, Plant
D013816 Thermodynamics A rigorously mathematical analysis of energy relationships (heat, work, temperature, and equilibrium). It describes systems whose states are determined by thermal parameters, such as temperature, in addition to mechanical and electromagnetic parameters. (From Hawley's Condensed Chemical Dictionary, 12th ed) Thermodynamic
D014326 Tropanes N-methyl-8-azabicyclo[3.2.1]octanes best known for the ones found in PLANTS. Azabicyclo(3.2.1)Octanes

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