Emerging supramolecular chemistry of gases

Molecular recognition of gases is an emerging area of chemistry. Supramolecular chemistry helps us to understand how gases interact with biological molecules and offers delicate insights into the mechanisms of their physiological activity. Principles of molecular recognition have been used for gas sensing, and have provided fundamental knowledge about the structure and dynamics of receptor-analyte complexes, and novel materials for gas sensing and storage have been developed. Supramolecular chemistry is also enabling us to learn how to transform gases into synthetically useful reagents. The rational design of novel catalysts for gas conversion and, more recently, encapsulation complexes with gases open novel directions in preparative synthetic chemistry.     

Nature of weak inter-and intramolecular interactions in crystals 6. Intramolecular O—H...O bond in enol forms of (phosphoryl)acylacetonitriles

The nature of the intramolecular O—H...O bond was studied and its energy was estimated by X-ray diffraction analysis and quantum-chemical calculations (B3LYP/6-311G**) of (diphenylphosphoryl)acylacetonitriles. The influence of the nature of the substituents at the double bond in the H-bonded ring and the crystal packing effects on the hydrogen bond were investigated. Dedicated to Corresponding Member of the Russian Academy of Sciences T. A. Mastryukova. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2406–2413, November, 2005.     

A simple method for the characterization of OHO-hydrogen bonds by H-solid state NMR spectroscopy

A set of OHO hydrogen bonded systems with known neutron diffraction structure has been studied by fast ¹H-MAS echo spectroscopy. It is shown that the application of a simple rotor synchronized echo sequence combined with fast MAS allows a faithful determination of the chemical shift of the proton in the hydrogen bond. Employing the empirical valence bond order model, the experimental ¹H chemical shifts of the hydrogen bonded protons are correlated to the hydrogen bond geometries. The resulting correlation between the proton chemical shift and the deviation of the proton from the center of the hydrogen bond covers a broad range of substances. Deviations from the correlation curve, which are observed in certain systems with strong hydrogen bonds, are explained in terms of proton tautomerism or delocalization in low-barrier hydrogen bonds. These deviations are a highly diagnostic tool to select potential candidates for further experimental and theoretical studies. Thus, the combination of the ¹H-MAS echo sequence with the correlation curve yields a simple and versatile tool for the structural analysis of OHO hydrogen bonds.     

19F and 1H NMR spectra of halocarbons

19F NMR chemical shifts and coupling constants are reported for 215 compounds. For 77 of these compounds, 1H NMR spectral data are also given. Long-range couplings, including 8J(F,F) and 5J(F,H), are reported. The complexity of halocarbon spectra owing to the presence of rotational isomers, asymmetric centers, long-range couplings, and chlorine isotope effects are illustrated, and the methods used for analyzing such complex spectra are briefly discussed.     

Carboxamides of Dihydropyridin-2(1<Emphasis Type="Italic">H</Emphasis>)-ones

Summary. 3-Carboxamides and 3-carboxanilides of 6-alkyl and 6-aryldihydropyridin-2(1H)-ones have been prepared via different reaction pathways. All synthesized amides show hydrogen bonds in their NMR spectra. The 4-hydroxy compounds were obtained as a mixture of tautomers. Their configurations were elucidated by NMR experiments.Received December 16, 2002; accepted December 20, 2002 Published online June 2, 2003     

Shape of the proton potential in an intramolecular hydrogen-bonded system. Part II

The crystals of 5,5′-dibromo-3-diethylaminomethyl-2,2′-biphenol N-oxide were studied by X-ray and FT-IR spectroscopy. Within this molecule two short OHO intramolecular hydrogen bonds are formed. The NO?H⁺?O⁻ bond between the OH and the N-oxide groups is very strong, of 2.419(7) Å between the oxygen atoms. The proton potential of this hydrogen bond is flat, broad and has probably no barrier—consequently it could not be located from X-ray diffraction data. The other hydrogen bond formed between two hydroxyl groups appears asymmetrical from FT-IR spectra, and shows also relatively limited proton polarizability. The molecular conformation is non-planar, due to strong overcrowding effect between the oxygen atoms involved in the hydrogen bonds.     

Is planarity of pyridin-2-yl- and pyrazin-2-yl-formamide thiosemicarbazones related to their tuberculostatic activity? X-ray structures of two pyrazine-2-carboxamide-N′-carbonothioyl-hydrazones

Crystal structures of two title compounds and several their relatives known earlier reveal conservative and characteristic features, which may be related to their tuberculostatic activity. The molecules are predominantly planar due to conjugation through five successive bonds in the zwitterionic fragment S⁻–C(sp²)–N–NH⁺–C(sp²)–NH₂ and intramolecular hydrogen bonds, which prevent rotation of the adjacent pyrazine (or pyridine) ring. It has been suggested that in spatial sense such planar molecules resemble acridines intercalating with nucleic acids and that similar process may be responsible for tuberculostatic activity of the title pyrazine-2-carboxamide-N′-carbonothioyl-hydrazones.     

Synthesis and Crystal Structure of a Vanadium(Ⅴ) Complex with 2-Hydroxy-1-naphthaldehyde Isonicotinoyl Hydrazone

The mononuclear vanadium(Ⅴ) complex with 2-hydroxyl-1-naphthaldehyde isoncotinoyl hydrazone was synthesized and characterized by single-crystal X-ray diffraction.The crystal is of monoclinic,space group P2 1/n with a = 10.3153(15),b = 7.4024(11 ),c = 24.413(4) (A),β= 101.911(2)°,V= 1824.0(5) (A)3,Z = 4,Mr = 427.28,Dc = 1.556 g/cm3,F(000) = 880,μ(MoKα) =0.591,the final R = 0.0372 and wR = 0.0926.The vanadium(Ⅴ) atom adopts a distorted square-pyramidal geometry coordinated by the tridentate ligand and two oxygen atoms.The hydrogen bonds and strong π…π stacking interactions link the complex molecules into a 3-D network structure.     

Weak dihydrogen bond interactions in organic crystals

Database analysis on H ? H interactions of the type CH₂ ? H₂C and N-H ? H-N in organic crystals substantiate the occurrence of dihydrogen bonds in the absence of metal atoms.