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.     

Corrugated single-layer graphite sheet as a model of stepped surface of a crystal

Electronic structure calculations have been performed for flat graphite sheets and periodically distorted sheets with different values of deformation angle and hydrogen adsorption. These characteristics do not all behave monotonically with increasing deformation angle. At small deformation angles, the electrons pass from the atoms of terraces to those of edges, while at larger angles the reverse pattern is observed. The position of the Fermi level also varies nonmonotonically. The binding energy of hydrogen depends significantly on the adsorption site, and the difference can be doubled. Based on the ata obtained, it was concluded that a priori statements derived from the “general concepts” on the difference in the physicochemical properties of, for example, terrace and edge atoms on high-index facets are unreliable.     

C–H· π Interaction and N·H–O Hydrogen Bonding in the Chair-like p-tert-Butylcalix[8]arene Complex Including Four Pyridine Molecules

Crystal structure analysis shows that the p-tert-butylcalix[8]arene host and its four pyridine guests sit around an inversion center in the P2₁/c crystal lattice. The monoclinic cell parameters and its volume are: a = 19.617(4), b = 9.912(2), c = 25.178(5) , = 101.03(3)°, V =4805.27(17) ³. For Z = 2 and Mw = 1614.18, the calculated density Dcalc = 1.116 g/cm³. A host calixarene molecule includes four pyridine guests in two different ways: by hydrogen bonding and by possible C–H· interaction between the molecules. The hydrogen bonding drives the host macrocycle into a chair-like conformation.     

Ligand dynamics and reactivity in trimetallic clusters

The general relationships between trinuclear cluster reactivity and the ligand dynamical processes in these systems are explored. Three specific mechanistic studies are presented: (1) the rate and stereochemistry of ligand addition to ₃-imidoyl complexes, (2) the factors influencing the rate of carbon-hydrogen bond activation in ₃-alkyne complexes, and (3) the origin of anomalously large kinetic deuterium isotope effect in metal to ligand and ligand to metal hydrogen transfer in trinuclear and binuclear complexes. In all three cases, the current state of the mechanistic studies are summarized and the possible rate of specific ligand dynamical processes in controlling the mechanism are put forth.     

从核磁共振氢谱推导的重质油氢碳原子摩尔比计算式

通过对炼油厂的催化油浆、重催油浆和催化重焦蜡油核磁共振氢谱中质子归属和重质油结构的假设，推导出计算这3种重质油的氢碳原子摩尔比计算式；结果表明，氢碳原子摩尔比的计算值与实测值非常接近，平均误差仅为3．1％。     

AN INVESTIGATION ON THE ab initio CALCULATION OF INTERMOLECULAR INTERACTION——NON-BONDED INTERACTION IN THE HYDROGEN BOND COMPLEX (HF)_2

An ab initio calculation of the hydrogen bond complex (HF)_2 is given with the 6-311 G~(**) basis set, according to which the potential surface around the balance point of the distancès and the orientations between two HF molecules is obtained. The atomic charges in the system are calculated with the PD/LSF method (potential-derived/least-square-fitting method) and then an analysis of the hydrogen bond interaction between two HF molecules is given with the (exp-6-1) potential function, by means of which it is shown that the main interaction between them is not an electro-static but a charge transfer one. The potential curve between two HF molecules is like a Morse function.     

Crystal Structures of 1,5,9,18,22,26-Hexaaza[11.11]-p-cyclophane Adducts; Two-dimensional Supramolecular Networks

Two newly identified supramolecular structures arise from self-assembly of the macrocyclic 1,5,9,18,22,26- hexaaza[11.11]-p-cyclophane salts with o-nitrophenol (C₂₈H₅₀N₆)⁴⁺·4(C₆H₄NO₂O)⁻ (1) and with HCl (C₂₈H₅₂N₆)⁶⁺·6Cl^-·4H₂O (2). In both cases two-dimensional supramolecular sheets are formed.     

Solid-state binding of dimethyl sulphoxide involving carboxylic host molecules. X-ray crystal structures of four inclusion species

The crystal structures of four dimethyl sulphoxide (DMSO) inclusion compounds with different carboxylic acid hosts,1–4, have been studied by single crystal X-ray analysis. Crystals of thetrans-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid inclusion compound (1a), [1 · DMSO (1: 1)] show monoclinic (P2₁/n) symmetry with the unit cell dimensionsa = 11.522(4),b = 18.658(2),c = 8.709(1) Å and = 98.92(2)°. The clathrate of the 9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid (2a), [2 · DMSO (1: 2)] is triclinic (P) with the cell dimensionsa = 15.043(7),b =9.657(4),c = 8.118(7) Å, = 101.81(5), = 96.05(4) and = 100.04(4)°. Triclinic (P) symmetry is shown also by the inclusion compound of 9,10-dihydro-9,10-ethanoanthracene-11-monocarboxylic acid (3a) [3 · DMSO (1:1)] with the cell dimensionsa=6.3132(1),b=7.9846(2),c=17.5314(4) Å, = 96.46(2), = 87.08(2) and = 106.02(2)°. The 9,9-bianthryl-2-monocarboxylic acid clathrate (4a) [4 · DMSO (1:1)] is monoclinic (P2₁/n) and the cell dimensions area = 19.625(18),b = 8.817(1),c = 14.076(8) Å and = 97.92(6)°. In all these structures, the hosts show the same basic recognition pattern for the DMSO guest, involving a strong O-H ... O bond from the COON to the S=O group, and a possible C-H ... O type interaction between the carbonyl O atom of the host and a CH₃ group of the guest. The crystals consist of discrete host-guest aggregates which are mainly held together by weak intermolecular interactions of the Van der Waals' type. The stoichiometries of the aggregates are, however, different.     

Synthesis and Crystal Structure of Tetraimidazolium Dinicotinatooctamolybdate

1INTRODUCTIONPolyoxometallates(POM)areofgreatinterestnotonlyfortheirstructuralvarietybutalsotheirunexpectedproperties[1,2].Theseinorganicanionshavebeenwidelyinvestigatedasdiversascatalysis,biology,medicine,magnetochemistryandmaterialscience[3～7].Thestudiesonthecoordinatedpoly-oxometallateswithorganicligandsmighthelptounderstandtherolesofpolyoxometallatesoncatalysis.Todate,aseriesofoctamolybdateswhichcanbedescribedas[Mo8O26X2]2n－4(nisthenormalchargeofthecoordinatedbaseX)havebeenreport…