Synthesis and crystal structure of copper complex of 7,16-bis(2-hydroxy-5-methyl-3-nitrobenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane

A lariat crown ether compound 7,16-bis(2-hydroxy-5-methylbenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane has been prepared via one-pot Mannich reaction. A copper(II) complex with the ligand 7,16-bis(2-hydroxy-5-methyl-3-nitrobenzyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane was unexpectedly synthesized and characterized by elemental analysis, IR and UV spectra. The crystal structure of the complex has been determined by X-ray diffraction. Both crystal structure analysis and spectroscopy study indicated that the side-arm phenols of lariat crown ether are nitrated while complexing with Cu(NO₃)₂. Structure shows that the copper(II) ion is coordinated to two nitrogen and four oxygen atoms, two from the crown ether and other two from the deprotonated phenolate groups. The coordination polyhedron is a distorted octahedron.     

Synthesis and crystal structure of 1,4,10,13-tetraoxa-7,16-diazoniumcyclo-octadecane bis(4-chloro-2-methyl-phenoxyacetate)

The title compound was prepared by the reaction of 1,4,10,13-tetraoxa-7,16-diazacyclo-octadecane with 4-chloro-2-methyl-phenoxyacetic acid in a ratio of 1:2. The structure has been proved by the data of elemental analysis, IR spectroscopy, NMR (¹H, ¹³C) technique and by X-ray diffraction analysis. Intermolecular hydrogen bonds between the azonium protons and oxygen atoms of the carboxylate groups were found. Immunoactive properties of the title compound have been screened. The compound has the ability to suppress spontaneous and Con A-stimulated cell proliferation in vitro and therefore can be considered as immunodepressant.     

大环镍配合物[Ni(teta)(NCS)2]的合成与结构研究

大环配体由于其独特的配位性能已吸引了广泛的注意,用大环化合物模拟生物功能,是当今大环化学发展的方向之一[1]。大环四胺配体5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四烷(简记为teta)的钴配合物已被用来作为研究维生素B12的模型分子[2],一些teta的配合物也已被陆续报道[3     

Ba(SbF(6))(2).5XeF(2): first xenon(II) compound with barium. Synthesis,vibrational spectra,and crystal structure

The reaction between Ba(SbF(6))(2) and excess XeF(2) in anhydrous HF at room temperature yields the white solid Ba(SbF(6))(2).5XeF(2) after the excess XeF(2) and the solvent have been removed under vacuum. Ba(SbF(6))(2).5XeF(2) crystallizes in the monoclinic space group C2/m, with a = 13.599(6) A, b = 12.086(4) A, c = 9.732(5) A, beta = 134.305(6) degrees, V = 1144.7 (8) A(3), and Z = 2. The coordination sphere of each barium atom consists of 12 fluorine atoms. The structure consists of alternating layers of Ba(SbF(6))(2).XeF(2) and 4 XeF(2) molecules. The Ba atoms in the Ba(SbF(6))(2).XeF(2) layer are in a nearly rhombic-net array and are linked with trans F-bridging ligands of SbF(6)(-). A XeF(2) molecule is placed in the center of each rhombus of the Ba(2+) array so that its symmetry axis is perpendicular to the plane of the Ba(SbF(6))(2).XeF(2) layer. This layer is linked to its neighbors by a layer of centrosymmetric XeF(2) molecules. Raman spectra are in accord with all XeF(2) molecules being symmetrical.     

The synthesis and crystal structure of [NiL(NCS)2] (L=3-hydroxyethyl-1,3,5,8,12-pentaazacyclotetradecane)

The reaction of H2CO and H2NCH2CH2OH with the nickel(II) complex of 1,9-diamino-3,7-diazanonane (2,3,2-tet) in the presence of Et3N gives the nickel(II) complex of the macrocycle 3-hydroxyethyl-1,3,5,8,12-pentaazacyclotetradecane (L), which can be readily isolated as the perchlorate salt. The reaction of KCNS with the perchlorate salt in aqueous solution gives [NiL(NCS)2] and the crystal structure of this complex has been determined. The complex is octahedral and trans with the two N-bonded thiocyanates in the axial sites with Ni-NCS bond lengths of 2.106 and 2.145AÅ. The equatorial sites are occupied by N2, N5, N8 and N12 with Ni-N bond distances of 2.053 to 2.076AÅ, which are typical for octahedral nickel(II) complexes. The ligand has a trans III configuration of the sec-NH centres, leading to chair six-membered rings and gauche five-membered rings. The hydroxyethyl group on N3 is axial. There is no evidence for hydrogen-bonding interactions involving the hydroxyethyl group in the crystal lattice.     

Cu（Ⅱ）-四氮杂十四环-NCS配合物的合成及其晶体结构

希夫碱以及希夫碱与金属离子的配合物具有较好的杀菌、抗癌和某些催化作用[1-3].在金属蛋白模型、磁性相互作用、分子识别,主客体化学以及电致发光、电子传送材料 [4-7]等方面有着十分重要的应用.     

Synthesis, Raman spectra and crystal structures of [Cu(XeF2)n](SbF6)2 (n=2, 4)

Pure [Cu(XeF2)2](SbF6)2 was prepared by the reaction of Cu(SbF 6) 2 with a stoichiometric amount of XeF2 in anhydrous hydrogen fluoride (aHF) at ambient temperature. The reaction between Cu(SbF6)2 and XeF2 (1:4 molar ratio) in aHF yielded [Cu(XeF2)4](SbF6)2 contaminated with traces of Xe 2F 3SbF6 and CuF2. The 6-fold coordination of Cu(2+) in [Cu(XeF2)2](SbF6)2 includes two fluorine atoms from two XeF2 ligands and four fluorine atoms provided by four [SbF6](-) anions. The neighboring [Cu(XeF 2)2](2+) moieties are connected via two [SbF6] units, with the bridging fluorine atoms in cis positions, into infinite [Cu(eta(1)-XeF2)2](cis-eta(2)-SbF 6)2[Cu(eta(1)-XeF 2)2] chains. Because of the high electron affinity of Cu(2+), coordinated XeF2 shows the highest distortion (Xe-Fb=210.2(5) pm, Xe-Ft=190.6(5) pm) observed so far among all known [M(x+)(XeF2)n](A)x (A=BF4, PF6, etc.) complexes. The four equatorial coordination sites of the Cu(2+) ion in [Cu(XeF 2) 4](SbF6)2 are occupied by four XeF 2 ligands. Two fluorine atoms belonging to two [SbF6] units complete the Cu (2+) coordination environment. The neighboring [Cu(XeF2)4](2+) species are linked via one [SbF6] unit, with bridging fluorine atoms in trans positions, into linear infinite [Cu(eta(1)-XeF2)4](trans-eta(2)-SbF6)[Cu(eta(1)-XeF2)4] chains. To compensate for the remaining positive charge, crystallographically independent [SbF6](-) anions are located between the chains and are fixed in the crystal space by weak Xe...F(Sb) interactions.     

Synthesis and crystal structures of schiff base copper(II) complexes [Cu(L1)(NCS)], [CuBr(L2)], and [CuCl(L3)]

A series of copper(II) complexes, [Cu(L¹)(NCS)] (I), [CuBr(L²)] (II), and [CuCl(L³)] (III), where L¹, L², and L³ are 2,4-dibromo-6-[(pyridin-2-ylmethylimino)methyl]phenolate, 4-chloro-2-[(pyridin-2-ylmethylimino)methyl]phenolate, and 1-[(pyridin-2-ylmethylimino)methyl]-naphthalen-2-ol, respectively, were prepared. The complexes were characterized by elemental analysis, IR spectra, and single crystal X-ray determination. The crystals of the three complexes crystalize in the monoclinic space group P2₁/n. For I, a = 8.127(2), b = 13.077(3), c = 14.967(3) Å, β = 91.975(2)°, V = 1589.8(6) ų, Z = 4. For II, a = 7.736(2), b = 10.613(2), c = 16.199(3) Å, β = 91.130(2)°, V = 1329.8(5) ų, Z = 4. For III, a = 8.062(2), b = 8.599(2), c = 21.087(2) Å, β = 100.338(2)°, V = 1438.1(4) ų, Z = 4. The Cu atom in each of the complexes is in square planar geometry.     

Coordinated and clathrated guests in the 3infinity[Hg6As4]4+ bicompartmental framework: synthesis,crystal and electronic structure,and properties of the novel supramolecular complexes [Hg6As4](CrBr6)Br and [Hg6As4](FeBr6)Hg0.6

Two new supramolecular complexes [Hg(6)As(4)](CrBr(6))Br (1) and [Hg(6)As(4)](FeBr(6))Hg(0.6) (2) have been prepared by the standard ampoule technique and their crystal structures determined. Both crystallize in the cubic space group Pa$\bar 3$ with the unit cell parameter a=12.275(1) (1) and 12.332(1) A (2), and Z=4. Their structures consist of bicompartmental, three-dimensional [Hg(6)As(4)](4+) frameworks with cavities of two different sizes occupied by guest anions of different type. The bigger cavities are filled with the octahedral MBr(6) (n-) ions (M=Cr or Fe; n=3 or 4), whereas the smaller cavities trap either Br- ions (1) or Hg(0) (2). The analysis of the host-guest contacts has allowed a classification of the octahedral guests as coordinated and the monatomic guests as clathrated. Magnetic measurements and ESR spectroscopy data have given information about the interaction between the host and guests. Band structure calculations (HF and hybrid DFT level) indicate that both 1 and 2 are non-metallic, with a band gap of approximately 1.5 eV (B3LYP), and that the interaction between the host and guests is of predominantly electrostatic character. It is shown that though the electrostatic host-guest interaction is weak it plays an important role in assembling the perfectly ordered supramolecular architectures.     

Synthesis, vibrational spectra, and crystal and molecular structure of copper 1,5-bis[2-(dihydroxyphosphinyl)phenoxy]-3-oxapentane dihydrate [Cu(H2L2)(H2O)2]

A new complex Cu(H₂L²)(H₂O)₂] (I), where H₄L² is 1,5-bis[2-(dihydroxyphosphinyl)phenoxy]-3-oxapentane, has been synthesized and characterized. Its molecular and crystal structure has been determined by X-ray crystallography and vibrational spectroscopy. In mononuclear complex I, the copper(II) cation is in a distorted square-planar environment of two water oxygen atoms and two oxygen atoms of the chelating dianion (H₂L²)^2?. The crystals are orthorhombic, space group Cmc2₁, a = 25.909(5) ?, b = 9.1500(18) ?, c = 8.5600(17) ?, V = 2029.3(7) ?³, Z = 4, ??_calc = 1.688 g cm^?3, ?? = 1.292 cm^?1; 3107 measured reflections, 1174 reflections with I > 2.0??(I), R _int = 0.0600, GOOF = 1.413, R ₁ (I > 2??(I)) = 0.0812, wR ₂ (I > 2??(I)) = 0.2145.     

Synthesis and crystal structure of new sodium oxothiocyanofluoroantimonate(III) Na2Sb5F9O3(NCS)2

Na₂Sb₅F₉O₃(NCS)₂, a new complex, has been synthesized from NaSCN and SbF₃ aqueous solutions and studied by chemical, X-ray diffraction, and thermal analyses and IR, ^121,123Sb NQR, and ¹⁹F NMR spectroscopy. Its layered structure (triclinic symmetry system, a = 6.9998(1) Å, b = 9.4180(1) Å, c = 13.1094(2) Å, α = 74.815(1)°, β = 78.188(1)°, γ = 82.779(1)°, Z = 2, space group P $\bar 1$ ) is built of Na⁺ cations and [Sb₁₀F₁₈O₆(NCS)₄]^4? decanuclear complex anions that consist of two [Sb₅F₉O₃(NCS)₂]^2? pentanuclear complex anions linked by two weak Sb-F ionic bonds (2.529(2) Å). Decanuclear complex anions are linked into layers by secondary Sb…F bonds and Na-F bonds. Van der Waals interactions link these layers into a framework. The complex is stable up to 200°C.     

The supramolecular assembly of tetraaqua-(pyridine-2,5-dicarboxylato)-copper(II) complex: crystal structure,TD-DFT approach,electronic spectra,and photoluminescence study

The copper(II) complex, {[Cu(2,5-pdc)(H₂O)₄]·H₂O} (1) [2,5-pdc?=?pyridine-2,5-dicarboxylate], has been synthesized and characterized by elemental analysis, IR spectroscopy, and X-ray crystallography. The metal shows a distorted octahedral coordination sphere and in solid state the complex forms a 3-D supramolecular network via hydrogen bonding and off-center anti-parallel π–π stacking interactions between py rings. At room temperature, 1 exhibits fluorescence in methanolic solution [λ_ex?=?226?nm, λ_em?=?309, 330, and 341?nm]. The geometry optimization at the B3LYP/LanL2DZ level led to a five-coordinate copper having a distorted square pyramidal geometry. The electronic spectrum of this compound is compared with the results obtained by employing density functional theory (DFT) and time dependent density functional theory calculations.     

Synthesis, structure, UV-Vis-IR spectra, magnetism and theoretical studies on Cu[(2-aminomethyl)pyridine](thiocyanate)2 and comparisons with an analogous Cu complex

The title complex was synthesized under self-assembly conditions using Cu(acetate)₂·H₂O, 2-amp (= 2-aminomethylpyridine) and KSCN, and was characterized by IR, elemental analysis and single crystal structural analysis, and its spectral and RT magnetic properties were investigated. The asymmetric unit consists of a square planar Cu(II) center, with two ligand N atoms and two anionic Ns forming the square plane. In the unit cell, the monomeric complex assembles into 2-D layers through very weak non-bonded interactions between anionic S and Cu²⁺. Further, the structure was satisfactorily modeled by calculations based on Density Functional Theory (DFT), and the UV-Vis and IR spectra are analyzed in depth with the help of Time Dependent DFT (TDDFT). The results indicate that the absorption maxima are at relatively high energy and are mainly assigned to π → π^∗ transitions (in pyridine), with a fair contribution of metal to ligand charge transfer (MLCT) and ligand to ligand charge transfer (LLCT) transitions. All the low lying transitions are categorized as mixed MLCT/LLCT. A very weak but broad band in the higher wavelength region has been detected and identified as a d-d transition band. Also, it has been found that when the ligand ratio is modified, the formation of Cu(2-amp)₂(SCN)₂ takes place under the same self-assembly conditions, whose structure only has been recently reported. Structural, spectral and theoretical comparisons are presented for both complexes.     

[Co（bim）x]配合物修饰的｛P2Mo5O23｝超分子的合成、晶体结构和电化学性质

利用水热技术合成了一种新型[Co(bim)x]配合物修饰的磷钼多金属氧酸盐超分子化合物[Co(bim)3] [Co(Hbim)2( H2 O) P2 Mo5 O23]·5H2O.通过元素分析、红外光谱、热重分析和X射线单晶衍射对化合物进行了表征.化合物属于单斜晶系,P2(1)空间群;晶胞参数:a=11.505 (2) nm,b=19.123 (3) nm,c=13.852(2) nm,α=90.00°,β=100.073(2)°,γ=90.00°,V=3 000.6(8)nm3,F(000)=1 756.0,Z=2.并测试了合成化合物的电化学性质.     

The double salt tris(diisopropylammonium) tetrachloridoferrate(III) dichloride: Synthesis, crystal structure, and vibrational spectra

Tris(diisopropylammonium)tetrachloridoferrate(III) dichloride crystallizes in the monoclinic space group P2₁/c (a = 7.6685(2) ?, b = 17.6079(3) ?, c = 23.3217(4) ?, β = 91.396(2)°, V = 3148.1(1) ?³, Z = 4, T = 113 K) with three diisopropylammonium cations (dip), one tetrachloridoferrate(III) anion, and two chloride anions in the asymmetric unit. The dip cations and the chloride anions form hydrogen bonded one-dimensional polymers along [010]. The tetrachloridoferrate(III) anion, habituated in between these chains, is not involved in any hydrogen bonding. The structural characterization is supported by infrared and Raman spectroscopic data.