First systematic investigation of C-H...Cl hydrogen bonding using inorganic supramolecular synthons: lamellar, stitched stair-case, linked-ladder, and helical structures

Using a group of six neutral M(II)Cl(2)-containing coordination compounds as building blocks, the first systematic investigation of C-H...Cl hydrogen-bonding interactions was performed. Single-crystal X-ray structural analyses of four new compounds (pseudo-tetrahedral Co(II) and Zn(II); distorted trigonal bipyramidal Zn(II)) authenticate the metal coordination geometry. To provide a unified view of the presence of noncovalent interactions in this class of compounds, we have re-examined the packing diagram of two previously reported compounds (a distorted square-pyramidal Cu(II) complex and a trans-octahedral Co(II) complex). The organic ligands of our choice comprise bidentate/tridentate pyrazolylmethylpyridines and an unsymmetrical tridentate pyridylalkylamine. This systematic investigation has allowed us to demonstrate the existence of versatile C-H...Cl(2)M interactions and to report the successful application of such units as inorganic supramolecular synthons. Additional noncovalent interactions such as C-H...O and O-H...Cl hydrogen bonding and pi-pi stacking interactions have also been identified. Formation of novel supramolecular architectures has been revealed: 2D lamellar (p-cyclophane) and 3D lamellar, 3D "stitched staircase" (due to additional hydrogen-bonding interactions by water tetramers, with an average O-O bond length in the tetramer unit of 2.926 A, acting as "molecular clips" between staircases), 3D linked ladder, and single-stranded 1D helix.     

STRUCTURE AND PROPERTIES OF P(MMA-MAA)/PEO INTERMACROMOLECULAR COMPLEX FORMED THROUGH HYDROGEN BONDING

The superstructure and properties of polymers might be improved and enhanced througl intermolecular complexation. In this paper, the preparation, structure and properties of P(MMA-MAA)/PEO intermolecular complex through hydrogen bonding are studied. By acid hydrolysis of PMMA, a series of P(MMA-MAA) copolymers have been prepared, the MAA content of which depends on the temperature and time of hydrolyzation. In case the MAA content in P(MMA-MAA) is beyond 0.4 mole fraction, the hydrogen bonding between P(MMA-MAA) and PEO is strong enough to form intermolecular complex. The supermolecular structure of the complex is quite different from that of its constituent, which was observed by an X-ray diffraction and transmission electron microscope. The crystallization of PEO is confined owing to complexation. The complex exhibits quite a lot of good properties in thermal stability, gas permeability as well as mechanical strength, and could be used in many fields.     

一系列氢键诱导液晶复合物的合成及表征

以２－氰基－３－（４－（２－氯－３－甲基－１－丁酰氧基）－苯基丙烯酸（Ａ）为质子给体，Ｎ－（４－吡啶基亚甲基）－４－烷氧基苯胺（ｎＳＳＺ）为质子受体，合成了一系列新的氢键复和物，经红外光谱证实了分子间氢键的存在，通过ＤＳＣ，偏光方法及Ｘ射线衍射方法对其液晶行为进行研究，结果表明复合物呈现近晶相行为。     

The properties of the metal complex hydrides

The essential features (geometries of the minima and of the saddle points, energy barriers) of the potential energy surface of the four hydrides YXH₄ mentioned in the title have been determined with two basis sets, of minimal and DZ quality respectively. The importance of the different extent of the deformation of the XH₄ group in the different structures of the four hydrides is brought out and discussed. The aspects of charge distribution and bonding are examined drawing on population analysis, comparison of the electrostatic molecular potentials and decomposition of the interaction energy (this last referred to the Y⁺ + XH ₄ ^– YXH₄ process). The capability of XH₃ in effecting the etherolytic disruption of the Y-H bond is finally brought out.     

Calix[4]arene-based ditopic receptor for dicarboxylates

Shape-selective recognition for the dicarboxylates in DMSO can be attained by a new calix[4]arene-based receptor 1 having two urea groups. Biologically active chorismate selectively bound in 1 over its dehydrated derivative. Molecular mechanics calculations gave a plausible explanation for the selective binding.     

Preparation and Properties of Aramid-Silica Hybrids with Inter-Phase Bonding Through (3-glycidoxypropyl)-trimethoxysilane

Nano-composites from aramid-silica system have been prepared via sol-gel process. Poly (phenyleneterephthalamide) copolymer chains were prepared by reacting a mixture of p- and m-phenylenediamines with terephthaloyl chloride in dimethylacetamide used as solvent. The sol-gel process in the polymer matrix was carried out through hydrolysis and condensation of a mixture of tetraethoxysilane and (3-glycidoxypropyl) trimethoxysilane. The latter was used to develop linkage, on one hand with silica network structure using alkoxy groups and on the other hand with aramid chains at its secondary amine groups through glycidal groups of silane. Mutual interaction between the two disparate phases aramid and silica network was thus created. Thin films of the composites containing different proportions of silica ranging from 5.0 to 25.0-wt% were cast by the solvent elution technique. The α-relaxation temperature associated with the glass transition was measured by the dynamic mechanical thermal analysis. The results showed an increase in the glass transition temperature from 328°C for the pure aramid to 352°C for the hybrid materials containing 25-wt% silica, an indicative of the increased interfacial interaction between the two phases. Films having relatively low silica content were flexible and transparent, but those with high silica content were opaque and brittle. These films were tested for their tensile strength, modulus and toughness. The mechanical strength of the composites as compared to the pure aramid increased initially but with further addition of silica the strength decreased. The initial increase can be explained due to increased interfacial interaction between the two phases, however agglomeration of silica particles was responsible for decreasing strength at higher silica contents.     

Evidence of a phase transition of RbHCO3 from high-resolution solid-state 13C and 87Rb NMR by comparison with KHCO3

A variable-temperature high-resolution 13C and 87Rb solid-state NMR study of powder rubidium hydrogencarbonate, RbHCO3, is presented for the first time. At ambient temperature, RbHCO3 is formed by centrosymmetric dimers linked by hydrogen bonds, but almost no information is available on this compound concerning proton disorder and the low-temperature phase. However, potassium hydrogencarbonate, KHCO3, which has an isomorphic structure for the high temperature phase, was well studied: it undergoes a non-ferroic, non-ferroelectric phase transition at Tc = 318 K between two monoclinic structures. The protons are disordered in an asymmetric double-well potential in the low-temperature phase, and the double-well potential becomes symmetric in the high-temperature phase. By comparison with recent solid-state NMR experimental results on KHCO3, we show that RbHCO3 undergoes a phase transition at Tc approximately 245 K, and give evidence that the proton dynamic disorder in both compounds is very similar.     

Hydrogen bonding in 2-hydroxy-benzhydrazide and 2-hydroxy-thiobenzhydrazide. Structural and spectroscopic study

Summary X-ray structural data are reported for 2-hydroxy-benzhydrazide(monoclinic; P2₁/n-C _2h ⁵ ;a=10.569(2) Å,b=11.264(2) Å,c=6.074(1) Å, =98.80(1)°;Z=4;R=0.054) and 2-hydroxy-thiobenzhydrazide (monoclinic; P2₁/n-C _2h ⁵ ;a=14.598(6) Å,b=5.975(2) Å,c=9.286(4) Å, =107.80(3)°;Z=4;R=0.044). In both compounds the phenolic OH groups are intramolecularly hydrogen bonded to the (thio)carbonyl oxygens and sulfurs, respectively; the basic intermolecular association patterns consist of closed six-membered hydrogen bonded dimers which are connected via N-H ... NH₂ hydrogen bonds. The spectral characteristics of the intramolecular O-H...O/S hydrogen bonds (solid state (OH)=2800/2700 cm^–1, CCl₄ solution (OH)=3035/3100 cm^–1, CDCl₃ solution (OH)=11.62/10.56 ppm) are similar to those of corresponding primary and secondary amides. The solid state IR spectra are consistent with hydrogen bonded NH groups and free NH₂ groups, the solution IR spectra indicate free NH₂ as well as free NH groups.

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Wasserstoffbrückenbindung in 2-Hydroxy-benzhydrazid und 2-Hydroxy-thiobenzhydrazid. Strukturelle und spektroskopische Untersuchungen

Zusammenfassung Es werden Röntgenstrukturdaten für 2-Hydroxy-benzhydrazid (monoklin; P2₁/n- C _2h ⁵ ;a=10.569(2) Å,b=11.264(2)Å,c=6.074(1)Å, =98.80(1)°;Z=4;R=0.054) und 2-Hydroxy-thiobenzhydrazid (monoklin; P2₁/n - C _2h ⁵ ;a=14.598(6)Å,b=5.975(2)Å,c=9.286(4)Å, =107.80(3)°;Z=4;R=0.044) berichtet. In beiden Verbindungen bilden die phenolischen OH-Gruppen intramolekulare Wasserstoffbrücken mit den Carbonyl-Sauerstoff-, bzw. den Thiocarbonyl-Schwefel-Atomen. Das intermolekulare Assoziationsmuster wird durch N-H...NH₂ Wasserstoffbrücken bestimmt, die jeweils zwei Moleküle über sechszählige Ringe zu Dimeren verbinden. Die IR- und NMR-spektroskopischen Charakteristika der intramolekularen O-H...O/S Wasserstoffbrücken (kristallin: (OH)=2800/2700 cm^–1, CCl₄-Lösungen: (OH)=3035/3100 cm^–1, CDCl₃-Lösungen: (OH)=11.62/10.56 ppm) sind sehr ähnlich zu denen entsprechender primärer und sekundärer Amide. Die Festkörper-IR-Spektren stehen in Einklang mit assoziierten NH- und freien NH₂-Gruppen, während die Lösungs-IR-Spektren auch auf das Vorliegen freier NH-Gruppen schließen lassen.

     

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.