Synthesis of Schiff Base-type Liquid Crystalline Crown Ethers Containing Dibenzo-18-Crown-6 Unit

The synthesis and characterization of novel Schiff base liquid crystalline crown ethers prepared from the intermediates 4-(4‘-alkoxylbiphenyl-4-carbonyl)benzaldehyde, cis- and trans-4,4‘-diaminodibenzo-18-crown-6 are described. The structure of these compounds have been well characterized by elemental analysis, IR, ^1H NMR and MS spectroscopy. The liquid-crystalline behavior of these compounds was also inverstigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) with a heating stage and polarimetric analysis.     

Synthesis and mesomorphic properties of 4-(4-bromopropyloxy)-4’-(4-alkyloxybenzylidene)anilines

This article describes the preparation and liquid crystalline properties of a new homologous series of 4-（4-bromopropyloxy）-4’- （4-alkyloxybenzylidene）anilines in which the phenyl ring is armed by a bromopropyloxy chain.The thermal behavior and mesomorphic properties of the synthesized compounds were studied with particular attention given to the correlation between their phase transition temperatures and anisotropic change influenced by molecular structure.All the members displayed enantiotropic smectic phase except for the homologue with the longest alkyloxy chain(R = C₁₈H₃₇),exhibiting only monotropic characteristic. The presence of bromine atom from the propyloxy side chain is found to be capable of altering and influencing the mesomorphic properties.     

[{Pt4(en)4(NHCOtBu)4}{Tl(18-crown-6)}2](PF6)6的合成与晶体结构

The compound [{Pt₄(en)₄(NHCO^tBu)₄}{Tl(18-crown-6)}₂](PF₆)₆ has been synthesized by a simple one-pot multicomponent reaction. Its structure was determined by X-ray single crystal diffraction analysis. The cation of the compound consists of one linearly arranged [Pt₄(en)₄(NHCO^tBu)₄]⁴⁺ chain and two [Tl(18-crown-6)]⁺ ions located at the two ends of the platinum chain. The complex crystallizes in a triclinic P1 with a=1.060 5(1), b=1.252 3(1), c=2.015(2) nm, α=107.430(2)°, β=91.032(2)°, γ=101.910(2)°, V=2.489 6(4) nm³, Z=2, R₁=0.074 4, wR₂(I>2σ(I))=0.222 5, S=1.062. CCDC: 294083.     

Syntheses,Crystal Structures and Magnetic Properties of Two New Low-dimensional Manganese (Ⅱ) Coordination Compounds

Two new low-dimensional Mn(Ⅱ) coordination compounds of Mn(H_2pimdc)_2(phen)(compound 1) and [Mn(Hpimdc)(phen)]n·nH_2O(compound 2) were synthesized, where H_3pimdc is a 2-propyl-imidazole-4,5-dicarboxylic acid and phen is 1,10-phenanthroline. Both compounds were thoroughly analyzed by X-ray single-crystal diffraction, element analysis, IR spectra, PXRD and thermal analysis. X-ray single-crystal diffraction analyses indicate that the phen ligands terminate metal ions on two sides to prevent the linkage between the neighboring metal ions into a higher dimensional structure in compounds 1 and 2. Compound 1 is constructed from mononuclear molecules which form the 1D helical supramolecular chain by N–H···O hydrogen bonds. In compound 2, Hpimdc is a tetradentate bridging ligand, which binds Mn(Ⅱ) ions to generate a single-stranded right helical chain parallel to the b axis. These 1D chains are additionally coupled by H-bonds as well as π···π stacking interactions, which formed a 3D supramolecular structure. Additionally, compound 2 demonstrated temperature-dependent magnetic susceptibility and negative value of θ(equal to –9.09 K), which is indicative of weak antiferromagnetic interactions between Mn(Ⅱ) ions.     

Three New Zn(Ⅱ)/Cd(Ⅱ) Coordination Polymers Constructed with 2-Mercaptonicotinic Acid and 1,2-Di(4-pyridyl)ethylene: Syntheses and Structure Analysis

Three new Zn(Ⅱ)/Cd(Ⅱ) coordination polymers based on 2-mercaptonicotinic acid (H2mna) with 1,2-di(4-pyridyl)ethylene (dpe) introduced as a bridging ligand have been synthesized via hydrothermal method and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. As reported in this paper, [Zn2(dpe)0.5(mna)2] (1) can be classified as a two-dimensional layer structure in which the 1D chain composed of Zn(Ⅱ) and mna ligands is bridged by dpe ligands, while the complex named [Zn4(dpe)4(mna)4] (2) is a tetra-nuclear cluster compound. These two compounds are further extended to three-dimensional structures by hydrogen bonds along with C-H…π and π…π interactions. Compound 3 with general formular [Cd2(dpe)0.5(mna)2]·H2O belongs to a three-dimensional porous structure in which the 2D metal layers formed by the coordination of Cd(Ⅱ) and mna ligands are connected with the bridging of dpe ligands.     

Syntheses,Crystal Structures and DNA-binding Properties of Zn(Ⅱ), Ni(Ⅱ) and Co(Ⅱ) Compounds Containing Thiazole Derivatives

Zn(Ⅱ), Ni(Ⅱ) and Co(Ⅱ) compounds(1～3) based on 2-(2-pyridyl)benzothiazole(bpt) and terephthalic acid(PTA) were synthesized. The crystal structures of [Zn(bpt)(PTA)2](1), [Ni(bpt)(PTA)2](2), and [Co(bpt)(PTA)2](3) have been determined by single-crystal X-ray diffraction analysis, which shows that all the three complexes belong to monoclinic system with space group P21/c. Time-dependent density functional theory(TD-DFT) calculation is performed on a reference structure of compound 3. The excited electrons mainly localized at the π* of ligand 2-(2-pyridyl)benzothiazole, which will be convenient for them to bind with the DNA reacting sites. Fluorescence spectroscopy, ultraviolet(UV) spectroscopy and viscosity were used to characterize the interaction of the compounds with Calf thymus DNA(CT-DNA). The results indicate that compounds 1～3 bind to CT-DNA and have a strong interaction with DNA. The compounds can probably bind to CT-DNA via a non-intercalative mode as concluded by studying the viscosity of a DNA solution in the presence of the compounds. This combination can effectively break DNA, which speculates that these three compounds may interact with the cancer cell DNA in this binding mode, thereby damaging the cancer cells.     

CRYSTAL AND MOLECULAR STRUCTURE OF [K(18-CROWN-6)][Bi(SCN)Cl_3]

<正> The crystal and Molecular structure of [K(18-crown-6)](Bi(SCN)Cl3] has been deterained by X-ray diffraction Method. Its crystal is triclinic, space group Pl,with a = 9.233(4), b = 11.661(5), c=11.738(5)A,a= 81.82(4)° ,β=71.47(4)°,γ=75.55(4)°, and Z = 2. The final structural refine-ment converged with unweighted and weighted R factors of 0.051 and 0.047 for 2924 observed reflections. Results of the structure analysis indicate that the K+ ion enters the cavity of the 18-crown-6 to form the complex cation and one Bi(Ⅲ) atom, one SCN ligand and three Cl atoms fora the anion. Each Bi(Ⅲ) atoa is coordinated by four Cl atoas, of which two are shared with other Bi(Ⅲ) atom, one N atom and one S atoa from two SCN ligands respectively shared with a third Bi(Ⅲ) atoa, forming octahedral geometry.     

POLYBINAPHTHYLS INCORPORATING (R)-2,2’-BINAPHTHO-20-CROWN-6 AND NAPHTHYL MOITIES

Chiral polymer was synthesized by the polymerization of （R）-6,6＇-bistributylstannyl-2,2＇-binaphtho-20-crown-6 （M-1） with 1,4-dibromo-2,3-bisbutoxy-naphthyl （M-2） by Pd（PPhs）4 catalyzed Stille coupling reaction. Both monomer and polymer were analyzed by NMR, MS, FT-IR, UV, polarimetry, DSC-TGA, CD, fluorescent spectroscopy and GPC. The major difference between monomer and polymer is that a long wavelength Cotton Effect was observed for the polymer due to its more extended conjugation in the repeating unit and a highly rigid backbone in the polymer chain. Polymer has strong blue fluorescence due to the efficient energy migration from the extended n-electronic structure of the repeating unit of the polymer to the chiral binaphthyl core and is expected to have potential application in the materials of fluorescent sensors and chiral chromatographic packing for resolution ofracemic amino acid.     

Synthesis,Crystal Structure,Vibrational Spectroscopy and Thermal Behavior of the First Alkali Metal Hydrated Hexaborate： K2[B6O9（OH）2]

New hydrated potassium hexaborate K2[B6O9（OH）2] has been synthesized under mild solvothermal conditions. The structure was determined by single-crystal X-ray diffraction and further characterized by FT-IR, Rarnan spectra and DTA-TG. It crystallizes in the monoclinic system with space group P21/n, a=0.9036（2） nm, b=0.66052（18） nm, c=1.5997（4） nm, β=91.862（4）°, V=0.9543（4） nm^3 and Z=4. Its crystal structure consists of K-O polyhedra and 1-D stepped polyborate chains constructed by new [B6O9（OH）2]2- fundamental building blocks. 1-D polyborate chains contain 3,8-membered boron rings. Adjacent chains are further linked via H-bonding interactions into 2-D layers. The K^＋ cations reside not only between the layers but also in the 8-membered boron rings of the chains, compensating the negative charges of the borate chains and holding the layers together into the 3-D structure through bonding with oxygen atoms of the chains.     

Crystal and Molecular Structure of BiCl3(15-Crown-5)

Single crystals of complex BiCl3(15-crown-5) were synthesized by gel method, and the structure was solved from X-ray diffraction data by direct and Fourier methods. The crystal is orthorhombic, space group is P212121 with unit cell parameters:a = 7. 677(4), 6=13. 254(6) and c= 15. 911(6) A , and 2=4. The final structural refinement converged with unweighted and weighted factors of 0. 053 and 0. 063 respectively for 1290 observed reflections. The structure consists of discrete BiCl3(15-crown-5) molecules in which bismuth atom is sandwiched between two essentially parallel planes, one of which contains five oxygen atoms and the other contains three chlorine atoms.     

Crystal Structure of 10-(2'''',5''''-Dimethoxybenzylidene) Anthrone

1 INTRODUCTION The 10-benzylidene anthrones which are important intermediate for organic syntheses[1～3] usually possess thermochromism[4] and photo- chromism[5], and have been found recently to have evident anti-cancer activity[6]. We found that the substituents in the phenyl ring will affect the bioactivity of those compounds. For more deeply investigating the structure-activity relationships (SAR) and understanding interactions between the three dimensional structure of the compound …     

Structure of Nb/Ta layered ternary tellurides containing first row transition metal atoms

A summary of research on the structure of Nb/Ta layered tellurides in the past period is reported. 14 compounds, which have been structurally characterized by X-ray diffraction work, are presented according to their structural features. The first two compounds, Nb2CrTe4 and Nb2Cu1.48Te4, are characterized in that the ternary atoms are inserted in the different layers from the Nb atoms. While in the other compounds, both kinds of metal atoms are inserted in the same layer. The six compounds with formula M2M'2Te4(M = Nb/Ta; M' = Ni, Co, Fe) are characterized in that their structure can be described as construction by using cluster units "M2M'2Te10" as building blocks. in the two metal-rich compounds, TaCo2Te2 and TaNi2Te2, Ta atom has a distorted mono-capped pentagonal prism configuration. The structure of TaFeTe3, TaNTe3 and NbNi2.34Te3 can be described as building by the arrangement of double octahedral chains (DOC), in this con-nection, a selenide Ta2Ni2Se5 is also included by using the second type of     

基于1,5,9-三硒杂[9]二茂铁环蕃的一维链状汞(Ⅱ)配位聚合物的合成与晶体结构(英文)

Amercury(Ⅱ)coordinationpolymerwith1,5,9-triselena[9]ferrocenophane(L),[HgI2L·0.5C4H4O·0.5CH3OH]n, has been synthesized and characterized. The X-ray crystal structure shows that bridging by the ligand L causes compound to form one-dimensional chain. The half-wave potential of 1,1′-ferrocenylene group is more negative than that of the "free" ligand, which reveals no through-space interaction Hg…Fe in the coordination polymers.     

Efficient and Facile Synthesis of ( ± )-Salvirecognine

Salvirecognine (7) is a diterpene isolated from Salvia recognita[1] which has been the subject of continued and growing interest, due to the range of biological activities shown by many members of this family. [2] In order to study further relationships between the structure and biological activity of the diterpene compounds and as an extension of diterpenoid synthesis in our laboratory, [3,4] the first total synthesis of the title compound was achieved by an efficient and facile route (Scheme 1).     

Synthesis and Crystal Structure of 2-(Diphenylphosphine oxide)-3-(diphenylphosphine oxide ethynyl) spiro [bicyclo[2.2.1]hepta-2,5-diene-7,1''''-cyclopropane]

1 INTRODUCTION Organic phosphine compounds always attract great interest for their unique properties and extensive uses in biochemistry, pesticide chemistry and synthetic organic chemistry. In the last two decades, much attention has been paid to phosphorus-containing olefin and acetylenic compounds for their applications in transition metal chemistry, asymmetric catalysis and photorearrang- ement [1~7 ]. Previously, we have reported the crystal structure of a novel host compound which …     

Synethesis and Crystal Structure of Bi(ethylenediamine)copper Tetracyanonickelate(Ⅱ)

The crystal structure of the title compound C8H16CuN8Ni has been determined by single crystal X-ray diffraction. The crystal is triclinic with space group P1, a=6.494(3), b=7.270(4), c=7.936(5) .A, α=106.67(3), β=91.33(4), γ=106. 80(6)°, V=341. 3(3) A3, Z==1, Mr=346. 54, F(000)=177, μ=2. 933mm-1, Dc= 1. 686 Mg/m3. The final R factor is 0. 0603 for 1214 unique ob24- served reflections [I≥2σ(I)]. The structure consists of [Cu(en)2]2+ (eh=ethylenedi amine) cations and [Ni(CN)4]2- anions linked together by two of the CN groups (the remaining two act as unidentate ligands) to form infinite chains, in the chain, the hy between the interchains also exist, with distances of 3. 160 and 3. 124 A , so it forms a three-dimensional structure of the title compound.     

N-乙基-1，10-菲罗啉-2-甲胺镍(Ⅱ)配合物的合成、晶体结构及性质研究(英)

A novel ligand N-ethyl-1,10-phenanthroline-2-methanamine and its Ni(Ⅱ) complex have been synthesized. The crystal structure of the complex has been determined by X-ray diffraction method. The Ni(Ⅱ) is five-coordinated by three nitrogen atoms from the ligand and two Cl^- anions in a distorted trigonal bipyramidal environment: the N(2), Cl(1) and Cl(2) in equatorial plane; the N(1) and N(3) in axial positions. The UV-spectra and IR-spectra of the ligand and its Ni(Ⅱ) complex were recorded and discussed. The thermodynamic properties of the ligand with various bivalent metals were studied by potentiometric titrations and the order of the stability constants is in agreement with the Irving-Williams order in coordination chemistry. CCDC: 221750.     

LOW-TEMPERATURE HEAT CAPACITY AND THERMODYNAMIC FUNCTIONS OF 2-CHLORO-6-(TRICHLOROMETHYL)PYRIDINE

The heat capacity of 2- chloro- 6- (trichloromethyl)pyridine has heen measured with anadiabatic calorimeter in the range from 13 to 316K. There is no indication of any phasetransition or thermal anomaly in this temperature region for the present compound. Theresults have been compared with those reported in [1] in the overlapping temperaturerange. The experimental heat capacity data have been fitted to a smoothed curve by the aidof the effective frequency distribution method, and the heat capacities below 13K have beenobtained by extrapolating the fitting curve down to 0K. The standard molar thermodynamicfunctions between 0 and 400 K have been derived by combining the present heat capacitymeasurements with the previous ones. The values of C_p~o (T), S~o(T) - S~o(0), [H~o(T) -H~o(0)]/T, and - [G~o(T) - H~o(0)]/T at T = 298.15 K are 189.35, 244.60, 112 .45 and 132.15J·K~(-1)·mol~(-1), respectively.     

Synthesis and structure of linear hexanuclear manganese (Ⅱ)benzoate cluster

From a reaction system including benzoic acid and Mn(NO3)2 in alkali medium, two hexanuclear manganese benzoate cluster compounds have been synthesized. A compound [Et4N]2[Mn6(PhCOO)14] has been structurally characterized, which contains hexanuclear Mn11 moieties extending unlimitedly to form one-dimensional linear structure. Carboxyl oxygen atoms are bridged in variety of modes to the Mn atoms, forming an arrangement like a sinusoid for the Mn atoms. The structural parameters of these compounds were compared with the data obtained from EXAFS determination for the Mn cluster in the OEC of PS11, supporting that the coordination sphere of the Mn site in the OEC may contain carboxyl bridges. The possible combination modes between the carboxyl group and the Mn atoms have been suggested. The NMR signals exhibit widening and shift produced by the influence of the paramagnetic Mn" sites. The red-shift of the absorption in IR spectrum was observed to be attributed to the coordination of the carboxyl group to the Mn     

分子模拟研究过渡金属锰(Ⅱ)取代的磷酸铝MnAPO-14

The structure of manganese(Ⅱ)-substituted aluminophosphate MnAPO-14 with AFN zeotype has been investigated by computational simulation in Cerius² package. Starting from reported structure of MnAPO-14, total 28 theoretical models of Mn-substituted AFN have been built and optimized to obtain their stable conformation. In terms of the host-guest non-bonding interaction and the framework energies, the Mn(Ⅱ)-substituted sites and the bonded sites of two H₂O molecules can be well predicted for MnAPO-14. The simulated structure is in good agreement with that of experimental MnAPO-14. Calculation results suggest that the replacement site of Al by Mn(Ⅱ) atom in AFN is dramatically effected by the guest molecules of organic templating resided in the channels, which is corresponding to the host-guest charge-density matching principle. This work will be helpful for the better understanding the structures of metal-substituted microporous materials.