Crystal and Species Engineering with Semi‐Flexible Nitrogen Containing Organic Cations: Generation of [H13O6]+ Ions with the Unfavoured Unbranched Topology by Enclosing Hydrochloric Acid in a Porous Inorganic‐Organic Hybrid Material

The reaction of rhodium(III) chloride trihydrate with 1, 4‐diazacycloheptane in concentrated hydrochloric acid results in the formation of tris(1, 4‐diazoniacycloheptane) hexaaquahydrogen(1+) bis(hexachlororhodate(III)) chloride, [C₅H₁₄N₂]₃[H₁₃O₆][RhCl₆]₂Cl ( 1 ). Dark red crystals of 1 are obtained by diffusion‐controlled crystallization at room temperature. Slow evaporation of the mother liquor over a period of several days yields a few tiny crystals of the bis(1, 4‐diazoniacycloheptane) hexachlororhodate(III) chloride hydrate, [C₅H₁₄N₂]₂[RhCl₆]Cl ˙ 1.75 H₂O ( 2 ), as red thin squared plates. In the context of crystal engineering, compounds 1 and 2 are inorganic‐organic hybrid materials built up from octahedral [RhCl₆]^3‐, simple Cl^‐ and semi‐flexible heterocyclic 1, 4‐diazoniacycloheptane ions, incorporating either the [H₁₃O₆]⁺ and further Cl^‐ ions or portions of simple water molecules. Both compounds crystallize in the space group type P2₁/c. Compound 1 contains isolated [H₁₃O₆]⁺ ions with a linear chain‐like configuration enclosed in the cavities of the inorganic‐organic framework. The presence of a strong central O···H···O hydrogen bond within the [H₁₃O₆]⁺ ions in 1 is confirmed by the short O···O separation of 2.47Å and by characteristic IR absorption bands at 1626 (s), ～ 1250 (m) and 668 (m) cm^‐1. During the thermal decomposition, compound 1 looses at first five equivalents of water and one equivalent of hydrochloric acid in a two‐step process at 37 °C and 67 °C. This is followed by the decomposition of the 1, 4‐diazoniacycloheptane cations and the hexachlororhodate(III) anions, starting at 190 °C and proceeding intensified at 240 °C.     

Crystal Engineering of Organometallic Compounds through Cooperative Strong and Weak Hydrogen Bonds: A Simple Route to Mixed-Metal Systems

Cooperative strong negatively charged and neutral O–H⋅⋅⋅O as well as weak charge-assisted C–H^δ+⋅⋅⋅O^δ− hydrogen-bonding interactions have been utilized for the crystal engineering of organometallic Fe^II/Co^III and Fe^II/Cr^I sandwich complexes. A section of the structure of [(η⁶-C₆H₆)₂Cr]⁺{[(η⁵-C₅H₄COOH)(η⁵-C₅H₄COO)Fe][(η⁵-C₅H₄COOH)₂Fe]_0.5}⁻ is shown in the picture.     

A novel three-dimensional cobalt (III) complex via hydrogen bonds: [Co(tacn)2] (ClO4)3 (tacn=1,4,7-triazacyclononane)

A novel cobalt (III) complex has been synthesized and its structure was determined. The structure consists of Co(tacn)₂³⁺ ions and ClO₄⁻, each cobalt (III) ion was six-coordinated with six nitrogen atoms of two tacns. Hydrogen bonds widely exist between the oxygen atoms of ClO₄⁻ and the nitrogen and carbon atoms of tacn, resulting in a unique three-dimensional network. The electronic spectra were measured and assigned in the strong-field approximation, giving the values of the parameter: Δ, B and C.     

Synthesis and Crystal Structure of a Complex of Melamine with Benzoic Acid

A new complex of melamine（MA） with benzoic acid（HBA） was prepared, affording [（HMA＋）（BA-）]-2H2O. Each HBA molecule is deprotonated and one triazine nitrogen atom of MA is protonated. The adjacent HMA＋ cations are related via an inverse center to form ribbons with a pair of N--H…N hydrogen bonds. COO- groups of BA- anions are hydrogen bonded to alternate sides of the （HMA＋）∞ ribbons to generate indention ID tapes, which are extended into a 3D structure via N--H…O- and N--H…OW hydrogen bonds and π-π stacking interactions. Predominant patterns of the hydrogen bond present in the complex are anion/water and amino/water tape structures. The hydrogen-bonding patterns consist of alternate 6, 10-membered rings sharing two edges. Infrared（IR） spectroscopy conforms that proton transfer has taken place in the complex.     

Synthesis and crystal structure of a new zinc diphosphonate

A new zinc diphosphonate [NH₃CH(CH₃)CH₂NH₃]₂Zn₂(edbbp)₂(HNO₃)₂·4H₂O [eddbp?= O₃PCH(Ph)NH(CH₂)₂NHCH(Ph)PO₃] was hydrothermally synthesized with Zn(NO₃)₂·6H₂O, ethane-1,2-diamino-N,N′-bis(benzylphosphonic acid) (H₄edbbp) and 1,2-propyldiamine. It consists of a centro-symmetric dimeric unit [Zn₂(edbbp)₂], in which each zinc ion adopts a distorted square-pyramidal coordination geometry. Hydrogen bonds formed between phosphonate groups and protonated 1,2-propyldiamine molecules link the dimeric units into one-dimensional chains. The doubly protonated 1,2-propyldiamine molecules serve not only as charge compensating counter ions, but also as bridging groups. Hydrogen-bonding interactions among the phosphonate oxygen atoms, water molecules, nitric acid molecules and protonated 1,2-propyldiamine result in the formation of a three-dimensional supramolecular network.     

2-甲氧基烟酸嘧霉胺盐晶体结构的研究

由嘧霉胺和2-甲氧基烟酸在乙醇介质中反应制得了化合物2-甲氧基烟酸嘧霉胺盐,经确证其晶体属于单斜晶系,空间群为P2(1)/n,a=1·0102(1)nm,b=0·7602(1)nm,c=2·3178(2)nm,β=96·74(2)°,V=1·7677(3)nm3,Dc=1·324g/cm3,Z=4,F(000)=744,μ=0·092mm-1,线性吸收系数μ(MoKα)=0·072mm-1。晶胞中不含结晶水,也不含配位水。每一个结构单元中有两个氢键,2-甲氧基烟酸嘧霉胺盐中不存在分子间氢键,主要靠范德华力在空间形成三维无限堆积结构。     

Miscibility Study of Blends of Polysulfone with a Methacrylamide Polymer Containing Quaternized Alkylammonium Sites

Abstract

Polymer films of polysulfone (PSF) and the copolymer poly(N,N‐[(dimethylamino)propyl] methacrylamide‐co‐methacrylamido propyl‐N,N‐dimethyl‐N‐dodecylammonium bromide), QPMADAP, containing a large fraction of dodecylammonium (36?mol%) groups, were prepared by film casting. The differential scanning calorimetry (DSC) investigation has shown that the miscibility behavior depends substantially on the solvent used. The introduction of QPMADAP in the PSF films does not lower the mechanical performance of the film, even if they contain up to 25% (w/w) QPMADAP, as evidenced by dynamic mechanical analysis (DMA) measurements. Moreover, the DSC and DMA investigation revealed a rather constant T _g depression of about 30°C, by the very first introduction of QPMADAP into the PSF matrix. FT‐Raman investigation of the surface of the solvent etched films verified that QPMADAP is not extracted by methanol. Furthermore, the morphological investigation by scanning electron micrography (SEM) revealed the formation of QPMADAP nanophases with dimensions less than 100?nm onto a PSF matrix.     

Synthesis and Physicochemical Characteristics of New Tetrachloroferrates(III) with Dimethylammonium Cation: X‐ray Crystal Structure of Bis(dimethylammonium) Chloride Tetrachloroferrate(III)

Two new tetrachloroferrates(III) have been synthesized of molecular formulas [(CH₃)₂NH₂][FeCl₄] and [(CH₃)₂NH₂]₂FeCl₅. The differences in their physicochemical properties have been highlighted using thermal analysis (TG‐MS) and differential scanning calorimetry (DSC). The crystal and molecular structure of [(CH₃)₂NH]₂FeCl₅ was determined. The iron(III) cation is four coordinated by chloride ions, and it adopts a slightly distorted tetrahedral coordination with three angles smaller and three larger than the tetrahedral one. In the structure four intermolecular N‐H···Cl hydrogen bonds link the [(CH₃)₂NH₂]⁺ cations to dimers via a Cl^? bridge.     

Interactions in Aqueous Mixtures of Alkylammonium Chlorides and Sodium Cholate

The interactions of alkylammonium chlorides (the number of carbon atom per chain was either 12, 14, or 16) with sodium cholate have been investigated by a combination of techniques including light and electron microscopy, surface tension, conductivity, light scattering, and microelectrophoretic measurements. The phase behavior has strongly depended on the molar ratio and actual concentration of oppositely charged surfactants. The change in the composition of the aggregates leads to a shape transformation from globular to elongated micelles to open and/or closed bilayers (vesicles) and precipitation. The length of micelles has been found to decrease dramatically with the concentration shift to the micellar regions of either surfactant. Upon a moderate excess of one surfactant, the mean hydrodynamic diameter of aggregates increases and wormlike micelles and/or open and closed bilayers are formed. Microscopic observations of alkylammonium cholates (novel catanionic surfactants precipitated in and/or close to equimolar region) have shown the presence of a variety of morphologies including twisted ribbons, tubules and bundles of tubules.     

Synthesis and crystal structures of new palladium catalysts for the hydromethoxycarbonylation of alkenes

The preparation and structural characterization of dimeric Pd(I)-Pd(I) complex [Pd₂{(PPh₃)(OSO₂CF₃)}₂].CH₂Cl₂ (1) and three palladium center [Pd₃{(PPh₃)(OSO₂CF₃)}₂] (2) and [Pd₃(PPh₃)₄](SO3CF₃)₂ (3) complexes are reported. The complexes exhibit coordination in which the phosphine phenyl ring is used to stabilize Pd(I) centers in (1) and, Pd(I) and Pd(0) centers in (2) and (3) by acting as π electron donors. The complexes were characterized by single crystal X-ray crystallography.     

Synthesis and Crystal Structure of di p Methyl pyridinium p methylpyridinidine Hexatungstate

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Crystal and Molecular Structure of Potassium trans-bis(iminodiacetato)-cobaltate(III)-2H2O

The combination of iminodiacetic acid (H₂ida) with cobalt(II) chloride hexahydrate in the presence of sodium hydroxide, followed by heating, produces the trans-facial isomer of K[Co(ida)₂]·2H₂O. This compound contains extensive intermolecular and intramolecular coordination and hydrogen bonding involving the potassium ions, and results in a complex three-dimensional structure in which each potassium ion is immediately surrounded by six cobalt centers.     

The structure and vibrational spectra of some ferroelectric and ferroelastic alkylammonium halogenoantimonates(III) and bismuthates(III)

Crystals from the rich family of alkylammonium halogenoantimonates(III) and bismuthates(III) containing small bioctahedra as well as infinite two- or one-dimensional polyoctahedral units attract particular attention from the point of view of possible applications. Such crystals exhibit a wealth of phase transitions including those to ferroelectric and ferroelastic phases. The analysis of vibrational spectra performed in this paper with respect to modes assigned to alkylammonium group shows that their interactions with polyanionic sublattice is of medium strength. The absorption pattern and particularly the splitting of bands on cooling very well correlates with other anomalies of physical properties and particularly with the behaviour of second moment of PMR lines and T₁ and T_1ρ relaxation times as functions of temperature. The temperature behaviour of modes is well described in terms of pseudospin–phonon coupling model that we presented for different modes in various crystals. The role of anionic dynamics is not sufficiently recognised but in one case, namely for the low temperature transition in (MA)₃Bi₂Br₉ crystal this role is predominant, according to vibrational and NQR spectra of methylammonium and isostructural caesium salt.     

Synthesis,Structure, and Polarized Optical Spectra of a New Fluoromanganate(III): [(H3N(CH2)2)2NH2]2[MnF5(H2O)]3

The synthesis and crystal structure of a new fluoromanganate(III), [(H₃N(CH₂)₂)₂NH₂]₂[MnF₅(H₂O)]₃, is reported. The unit cell is unusually large: monoclinic, P2₁/c (no. 14), a = 41.0512(13) Å; b = 9.6469(4) Å; c = 12.8021(7) Å; β = 91.927(4)°; Z = 8, R = 0.0627 and wR₂ = 0.1347. The [MnF₅(H₂O)]^2– anions are octahedral with a strong distortion along the F–Mn OH₂ axes due to the Jahn-Teller effect. A very rich intermolecular hydrogen bond framework is present, leading to chains of octahedra linked by double-hydrogen bonds. The polarized optical spectra on single crystals are explained in terms of the intraconfigurational d⁴ transitions split by a ligand field of C_4v symmetry.     

Syntheses and crystal structures of two 2D coordination polymers of cobalt(II) and nickel(II) with the Malonate Dianion Ligand

Two 2D complexes, [Co(mal)(phen)(H₂O)₂] (1) and [Ni(mal)(phen)(H₂O)₂] (2) (mal?=?malonate dianion; phen?=?1,10-phenanthroline), have been synthesized by the reaction of Co(ClO₄)₂·6H₂O and Ni(ClO₄)₂·6H₂O with disodium malonate and 1,10-phenanthroline in MeOH/H₂O solution. Their crystal structures have been determined by X-ray diffraction. The structures of Complexes 1 and 2 show that each metal ion is coordinated by one 1,10-phenanthroline, two water molecules and a malonate ligand forming a distorted octahedral environment and each mononuclear fragment forms a 2D supramolecular network through H-bonding interactions.     

Crystal Structure,Phase Transition and Ferroelastic Properties of [N(CH3)4]3[As2Cl9]

The crystal structure of [N(CH₃)₄]₃[As₂Cl₉] is determined at 293 K. It crystallizes in trigonal space group P31c: a = 9.2199(8), c = 21.065(3)Å, Z = 2, R₁ = 0.0505, wR₂ = 0.1283. The crystal is built of the discrete bioctahedral [As₂Cl₉]^3— anions and the deformed tetramethylammonium cations. A structural phase transition in [N(CH₃)₄]₃[As₂Cl₉] is detected by the DSC and dilatometric techniques at 146/151 K (on cooling/heating). Dielectric relaxation studies in the frequency range 75 kHz — 5 MHz indicate reorientations of the tetramethylammonium cations within the high temperature phase. Optical observations show the existence of the ferroelastic domain structure below 146 K. The possible mechanism of phase transition is discussed on the basis of the presented results.     

烷基氯化铵体系中分子有序组合体的转化

采用动态光散射、吸收光谱、粘度及电镜透射等方法研究了烷基氯化铵在弱碱性条件下溶液浓度变化对分子有序组合体结构的影响.当表面活性剂浓度大于cmc时,分子有序组合体的形态随表面活性剂浓度的增加出现胶团-囊泡-球状胶团的转化过程,这与水解产生的极性有机物烷基胺量的变化密切相关.     

Cobalt(III) Supramolecuar Complex: Synthesis,Crystal Structure and Anions Recognition Properties of 6,7-Dinitroquinoxaline-2,3-dione

A 3D supramolecular complex [Co(III)(Phen)₂Cl₂][DNQ]Cl·H₂O (DNQ = 6,7-dinitroquinoxaline-2,3-dione) has been synthesized and determined by single-crystal X-ray analysis. Anion binding studies carried out using ¹H NMR and UV-visible revealed that a genuine hydrogen bond interaction between anion receptor 2 and Cl^?  can be detected, but fluoride is deprotonating the anion receptor 2. X-ray analysis results show that it is not possible for the two amide nitrogen atoms of anion receptor to form hydrogen bonds to a chloride ion in the presence of small aliquots of water.     

Crystal Structure Investigations on Imines derived from 3‐Ferrocenyl‐prop‐2‐enal Crystallizing in Non‐centrosymmetric Space Groups

The condensation of 3‐ferrocenyl‐prop‐2‐enal with primary amines leads to the formation of the corresponding imines in good yields. The crystal structures of imines derived from p‐dimethylamino‐aniline and furfurylamine are determined by the ability of the functional groups to act as hydrogen bond donor or acceptor sites. Although N, N‐dimethyl‐N′‐(3‐ferrocenyl‐allylidene)‐benzene‐1, 4‐diamine and furan‐2‐ylmethyl‐(3‐ferrocenyl‐allylidene)‐amine are achiral molecules they crystallize in the non‐centrosymmetric space groups P2₁ and Pca2₁, respectively. The molecular architecture of N, N‐dimethyl‐N′‐(3‐ferrocenyl‐allylidene)‐benzene‐1, 4‐diamine is realized by the incorporation of dichloromethane acting as hydrogen bond donor and acceptor with both hydrogen and both chlorine atoms. On the other hand, the molecules of furan‐2‐ylmethyl‐(3‐ferrocenyl‐allylidene)‐amine are linked by hydrogen bonds towards the centroid of one of the cyclopentadienyl ligands and towards the oxygen atom of the furan ring to produce infinite chains.