Ph[PhC(O)NH]2P=NC(O)Ph: a new mesomeric stabilized azaylide. Synthesis, crystal structure and IR spectroscopic results

The structure of Ph[PhC(O)NH]₂P=NC(O)Ph (2) in solid state and in solution is discussed on the basis of a crystal structure analysis and IR and Raman spectra. In crystalline state 2 forms dimers which are associated via two pairs of bifurcated (N–H)₂O=C hydrogen bonds. The spectroscopic data are in good agreement with the crystallographic results with respect to the hydrogen bonding and they suggest that 2 also in solution is associated.     

Low-temperature single crystal X-ray diffraction and high-pressure Raman studies on [(CH3)2NH2]2[SbCl5]

The structure of bis(dimethylammonium) pentachloroantimonate(III), [(CH₃)₂NH₂]₂[SbCl₅], BDP, was studied at 15 K and ambient pressure by single-crystal X-ray diffraction as well as at ambient temperature and high pressures up to 4.87(5) GPa by Raman spectroscopy. BDP crystallizes in the orthorhombic Pnma space group with a=8.4069(4), b=11.7973(7), c=14.8496(7) Å, and Z=4; R₁=0.0381, wR₂=0.0764. The structure consists of distorted [SbCl₆]³⁻ octahedra forming zig-zag [{SbCl₅}_n]²ⁿ⁻ chains that are cross-linked by dimethylammonium [(CH₃)₂NH₂]⁺ cations. The organic and inorganic substructures are bound together by the N-H…Cl hydrogen bonds. The distortions of [SbCl₆]³⁻ units increase, partly due to the influence of the hydrogen bonds which became stronger, with decreasing temperature. The preliminary room temperature, high-pressure X-ray diffraction experiments suggest that BDP undergoes a first-order phase transition below ca. 0.44(5) GPa that destroys single-crystal samples. The transition is accompanied by changes in the intensities and positions of the Raman lines below 400 cm⁻¹.     

OH stretch IR spectra of (H2O)3 and benzene-(H2O)3

The OH stretch IR spectrum of (H₂O)₃ is significantly altered upon complexation of the cluster with a benzene molecule. Theoretical calculations show that the differences in the OH stretch spectra of (H₂O)₃ and benzene-(H₂O)₃ are primarily due to mode localization induced by the benzene molecule. Received: 27 January 1997 / Accepted: 28 January 1997     

Stabilisation of heterobimetallic networks by crown ethers and hydrogen-bonding in [Ni(H2O)6][Cu3Cl8(H2O)2] · (15-crown-5)2 · 2H2O: Structure and magnetism

[Ni(H₂O)₆][Cu₃Cl₈(H₂O)₂] · (15-crown-5)₂ · 2H₂O can be conveniently prepared by the interaction of NiCl₂ · 6H₂O, CuCl₂ · 2H₂O and 15-crown-5 in water. The X-ray crystal structure reveals an ionic complex involved in a hydrogen-bonded two dimensional network with the [Ni(H₂O)₆]²⁺ and [Cu₃Cl₈(H₂O)₂]²⁻ ions sandwiched between the 15-crown-5 macrocycles. The magnetic susceptibility data (4–300 K) and magnetisation isotherms (2–5.5 K; 0–5 T) are best interpreted in terms of intra-trimer ferromagnetic coupling within the [Cu₃Cl₈(H₂O)₂]²⁻ moieties, with J ∼ 6 cm⁻¹, and antiferromagnetic coupling between the trimers, the latter mediated by H-bonding pathways. Comparisons are made to other reported quaternary ammonium salts of [Cu₃Cl₈]²⁻ and [Cu₃Cl₁₂]⁶⁻, most of which display structures that involve close stacking of such Cu(II) trimers, rather than being of the present isolated, albeit H-bonded, types.     

Dimeric Sandwich‐like Ion Pairs in the Crystal Structure of Tetrabutylammonium Ozonide Ammoniate

The novel ionic ozonide {[N(C₄H₉)₄](O₃)}₄·4.75NH₃ was synthesized by ion‐exchange reaction in liquid ammonia. The crystal structure was determined by single crystal diffraction at 100 K (monoclinic space group P2₁, a = 15.014(11) Å, b = 13.696(10) Å, c = 19.890(15) Å, β = 105.407(12)°, V = 3943(5) ų, Z = 2). The structure consists of a packing of sandwich‐like dimeric ion pairs in which two ozonide anions are interspersed between two tetrabutylammonium cations. Ammonia molecules from the solvent are localized in cavities in the structure. They are involved in hydrogen bonding with the ozonide ions. The desolvated tetrabutylammonium ozonide forms stable solutions in dichloromethane which may open up novel possibilities of tapping into the synthetic potential of the ozonide ion.     

Molecular Dipole Moment and Interaction Dipole Moment in 2-N-Substituted Amino-3(or 5)-methyl-4-nitropyridines and Their N-Oxides

The dipole moments of 2-alkylaminoand 2-alkylnitramino-3(or 5)-methyl-4-nitropyridines and their N-oxides have been measured, as well as calculated, using vectorial summation of the group moments and by ab initio method. The estimated interaction dipole moments, _int, have been discussed in terms of the electronic and steric effects and intramolecular hydrogen bonding. Introduction of the NHCH₃ group to position 2 in 4-nitropyridine strengthens the conjugation between the nitro group and ring nitrogen. The lack of such strengthening in 4-nitropyridine-N-oxides is explained as being due to formation of intramolecular hydrogen bond between the N-oxide group and the hydrogen of alkylamino group. Introduction of the nitramino group does not lead to marked modification of the charge distribution in a molecule. This fact may be explained by much weaker electron-donating ability of this group in comparison with the alkylamino group.     

3D H-bonding networks self-assembly from pyridinium derivatives and bis(maleonitriledithiolato)zincate(II)

The two ion-pair complexes, [pyH]₂[Zn(mnt)₂] (1) and [4,4′-bipyH₂]-[Zn(mnt)₂] (2), were synthesized, where mnt²⁻ denotes maleonitriledithiolate, and [pyH]⁺, [4,4′-bipyH₂]²⁺ represent pyridinium and diprotonated 4,4′-bipyridinium, respectively. Their single crystal structures show that there are strong bifurcated H-bonding interactions between the cations of the pyridinium derivative and the [Zn(mnt)₂]²⁻ anions in both 1 and 2. The bifurcated H-bonding interactions between the N–H of the pyridiniums and the CN groups of the mnt²⁻ ligands give rise to a 2D layered H-bonding network, the adjacent layers come together in such way as mutual embrace to give a tight pack, thus 2D hydrogen-bonding sheets further develop into 3D H-bonding networks through weak C–HS and ππ stacking interactions in 1. As for 2, the cations and anions connect into several types of H-bonding macrorings ([2+2], [3+3] and [4+4]), these H-bonding macrorings fuse to extend into 2D layered structure, the interpenetration between [3+3] and [4+4] type H-bonding macrorings in the adjacent layers give further rise to novel 3D extended H-bonding networks, in which there are clearly parallel stacks of cations and the chelate rings of anions.     

Molecular mechanics (MM3) calculations on lithium amide compounds

The MM3 force field has been extended to deal with the lithium amide molecules that are widely used as efficient catalysts for stereoselective asymmetric synthesis. The MM3 force field parameters have been determined on the basis of the ab initio MP2/6-31G* and/or DFT (B3LYP/6-31G*, B3-PW91/6-31G*) geometry optimization calculations. To evaluate the electronic interactions specific to the lithium amides derived from the diamine molecules properly, the Lewis bonding potential term for the interaction between the lithium atom and the nonbonded adjacent electronegative atom such as nitrogen was introduced into the MM3 force field. The bond dipoles were evaluated correctly from the electronic charges on the atoms calculated by fitting to the electrostatic potential at points selected. The MM3 results on the molecular structures, conformational energies, and vibrational spectra show good agreement with those from the quantum mechanical calculations.     

A MORPHOLOGICAL STUDY OF POLY（DIVINYLBENZENE-co-ACRYLIC ACID） IN CROSSLINKING PRECIPITATION POLYMERIZATION

Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobutyronitrile） （AIBN） as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units.     

次级键与晶体中锑(III)螯合物配位多面体研究

考虑立体活性孤对电子附近次级键配位原子的贡献, 对文献报道的三十个氨基多羧酸锑(III)螯合物的晶体结构中配位多面体描述进行了全面的修正. 配位多面体的几何构型指定采用了单位球内截多面体的两面角判据及其相关的ANVPDA程序. 所有配位多面体几何构型的修正均得到了键价计算的有力支持.