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1.
The 2,11-dithia[3.3](3,5)pyrdinophane (L1) has been synthesized by a new method and characterized by 1H NMR, which is used to form coordination complexes C14H14N4O6S2Ni (I) by addition of Ni2+ cation and C14H14N3O3S2Ag (II) by addition of Ag+ cation. 2,11,20-Trithia[3.3.3](3,5)pyridinophane (L2) and 2,11,20,29-tetrathia[3.3.3.3](3,5)pyridinophane (L3) have also been synthesized as by-products. Single-crystal X-ray analysis reveals that the conformation of the L1 is syn(boat-chair), complexes I and II also adopt syn(boat-chair) (CIF files CCDC nos. 1400332 (I) and 700724 (II)). While in I, Ni(II) is coordinated with L1 with two nitrogen and four oxygen atoms, in II, Ag(I) is coordinated with L1 by two nitrogen and two sulfur atoms came from four ligands. In complexes I and II, the formation of three-dimensional structure depends on π???π stacking and hydrogen bonds.  相似文献   

2.
Four new complexes, [Cu2(Bpca)2(L1)(H2O)2] · 3H2O (I), [Cu2(Bpca)2(L2)(H2O)2] (II), [Cu2(Bpca)2(L3)] · 2H2O (III), [Cu2(Bpca)2(L1)(H2O)] · 2H2O (IV) (Bpca = bis(2-pyridylcarbonyl)amido, H2L1 = glutaric acid, H2L2 = adipic acid, H2L3 = suberic acid, H2L4 = azelaic acid) have been synthesized and characterized by single-crystal X-ray diffraction methods (CIF files CCDC nos. 1432836 (I), 1432835 (II), 817411 (III), and 817412 (IV)), elemental analyses, IR spectra. Structural analyses reveal that compounds I, II, and IV have similar structures [Cu(Bpca)]+ units bridged by dicarboxylate forming dinuclear units, whereas the dinuclear of compound III are edge-shared through two carboxylate oxygen atoms of different suberate anions. Hydrogen bonds are response for the supramolecular assembly of compounds I to IV. The temperature-dependent magnetic property of III was also investigated in the temperature range of 2 to 300 K, and the magnetic behaviour suggests weak antiferromagnetic coupling exchange.  相似文献   

3.
Seven new cobalt(II) complexes based on the Schiff bases, 2,6-diacetylpyridine bis(isonicotinoylhydrazone) (H2L1) and 2,6-diacetylpyridine bis(nicotinoylhydrazone) (H2L2), are synthesized and studied by X-ray diffraction analysis: [Co(H2L1)(NCS)2] · 2.25H2O (I), [Co(H2L2)(NCS)2] · CH3OH (II), [Co(H2L2)(NCS)(H2O)]NCS (III), [Co(H4L1)(NCS)2](NO3)2 · 2H2O (IV), [Co(H4L1)(NCS)2][Co(NCS)4] · 0.75H2O (V), [Co(H4L2)(NCS)2][Co(NCS)4] · 1.75H2O (VI), and [Co(H2L2)(NCS)(CH3OH)]2[Co(NCS)4] · 2CH3OH (VII) (CIF files CCDC 941186 (I), 1457906 (Ia), 1457905 (II), 941187 (III), 1457907 (IV), 1457908 (V), 1457909 (VI), and 941188 (VII)). The organic ligands in the complexes act as pentadentate neutral H2L or doubly protonated (H4L)2+ coordinated through the same set of donor atoms N3O2. In all compounds IVII, the coordination polyhedron of the Co2+ ion in a complex with the Schiff bases has a shape of a pentagonal bipyramid. The hydrazones are arranged in the equatorial plane of the bipyramid. Its axial vertices are occupied by the nitrogen atoms of the NCS ̄ anions in compounds I, II, and IV–VI and by the nitrogen atoms of NCS ̄ and oxygen of the water molecule in compound III or methanol in compound VII. The NO 3 - anions or [Co(NCS)4]2 ̄ complex anions obtained by the reactions are involved along with the NCS ̄ anions in the formation of compounds IV–VII.  相似文献   

4.
Hydrothermal reaction of Co(II) salt with 1,4-di(1-imidazolyl)benzene (L1) and 4,4’-oxydiphthalic acid (H4OA) yields a new complex [Co3(HOA)2(L1)4(H2O)4] (I). [Ni(L2)2SO4] · 0.5H2O (II) can be obtained via the hydrothermal reaction of NiSO4 · 6H2O with 1,3-di(1H-imidazol-4-yl)benzene (L2). Complexes I and II have been characterized by single-crystal and powder X-ray diffraction (CIF files CCDC nos. 1019291 (I) and 1019292 (II)), IR, elemental, and thermogravimetric analyses. Complex I exhibits the uninodal six-connected 3D pcu framework structure of I with (412 · 63) topology; Complex II consists of the uninodal four-connected 2D sql (44 · 62) networks. In addition, magnetic property of I was investigated.  相似文献   

5.
Three two-dimensional coordination polymers [Cd(2,3-Pyma)Cl2] n (I), {[Cd(2,3-Pyma)(1,4-Chdc)] · 4H2O}n (II) and {[Zn2(2,3-Pyma)(1,2,4,5-Bttc)(H2O)4] · 6H2O} n (III) (2,3-Pyma = (2,3-pyridylmethyl) amine, H2-1,4-Chdc = 1,4-cyclohexanedicarboxylic acid, and H4-1,2,4,5-Bttc = 1,2,4,5-benzenetetracarboxylic acid) have been synthesized and structurally characterized by single crystal X-ray crystallography (CIF files CCDC nos. 989461 (I), 1055685 (II) and 1055686 (III)). Three complexes are all twodimensional layer networks bridged by the flexible 2,3-Pyma ligands or the carboxylate ligands. It is noted that the flexible 1,4-Chdc ligands bind the Cd2+ ions into a helical chain structure in complex II. The photoluminescence and thermal properties are investigated.  相似文献   

6.
Complexes [CuL1Cl2] (I), [CuL2Cl2] · EtOH (II), and Cu2L3Cl4 (III) containing esters of the N-derivatives of optically active amino acids based on (+)-3-carene (L1, L2) and (?)-α-pinene (L3) are synthesized. The crystal and molecular structures of compounds I and II are determined by X-ray diffraction analyses (CIF files CCDC nos. 1560071 (I), 1560072 (II)). The crystal structure of compound I consists of mononuclear complex molecules. In the structure of compound II, the unit cell contains two crystallographically independent molecules of mononuclear complex [CuL2Cl2] and two EtOH molecules. Ligands L1 and L2 perform the tridentate-chelating function by the N atoms of the NH and NOH groups and by the O atom of the C=O group. In compounds I and II, the coordination polyhedra Cl2N2O of the Cu atoms are trigonal bipyramid. According to the data of IR and electronic spectroscopy, binuclear complex III has similar coordination polyhedra. The experimental values of μeff for compounds I, II, and III at 300 K are 1.93, 1.88, and 2.71 μB. For complex III, the μeff(T) dependence in a range of 2–300 K indicates a weak ferromagnetic exchange interaction.  相似文献   

7.
The procedures for the synthesis of the Cu(II) complexes with bis(pyrazole-1-yl)methane (L1), bis(3,5-dimethyl-4-bromopyrazole-1-yl)methane (L2), and bis(3,5-dimethyl-4-iodopyrazole-1-yl)methane (L3) of the composition Cu2(L1)2Br4 (I), Cu2(L2)2Cl4 (II), Cu(L3)(NO3)2 (III), and Cu(L3)(H2O)(NO3)2 · 2H2O (IV) were developed. The organic ligands in the above complexes are coordinated to Cu(II) in a bidentate cyclic type through the N(2), N(2′) atoms of the pyrazole rings. The molecular and crystal structures of L2, L3, II, III, and IV were determined by X-ray diffraction. The study of the μeff(T) function in a temperature interval 2–300 K showed that compound I, which exhibited ferromagnetic exchange interactions in the chains, undergoes transition to antiferromagnetic state with weak ferromagnetism. The exchange antiferromagnetic interactions predominate in compound II.  相似文献   

8.
The syntheses of a mononuclear zinc(II) complex [ZnCl(L1)(Amp)] (I) and a mononuclear nickel(II) complex [Ni(L2)(HL2)](BF4) · 0.5H2O (II) (HL1 = 4-methyl-2-[(4-methylpyridin-2-ylimino) methyl]phenol, HL2 = 4-methyl-2-[(pyridin-2-ylmethylimino)methyl]phenol; Amp = 2-amino-4- methylpyridine) were prepared under microwave irradiation. The complexes were characterized by a combination of elemental analyses, and IR and electronic spectra. Their structures were further confirmed by single crystal X-ray crystallography (СIF files CCDC nos 1437737 (I), 1437738 (II)). The Zn atom in the monomeric complex I is in tetrahedral coordination. The Ni atoms in the dimeric complex II are in octahedral coordination. Crystals of the complexes are stabilized by hydrogen bonds. In order to evaluate the biological activity of the complexes, in vitro antibacterial against Staphylococcus aureus, Bacillus subtilis, Escherichia coli, and Pseudomonas aeruginosa was assayed. The complexes have strong activity against Bacillus subtilis.  相似文献   

9.
Four d 10-based complexes with chemical formulae {[Zn(L1)2(H2O)2(4,4′-Bipy)2] (I), {[Zn2(L1)4(Mi)] · 4H2O} (II), {[Zn(L1)2(Phen)] · H2O} (III) {[Cd(L1)2(Phen)] · 2H2O} (IV) (HL1 = p-hydroxy phenylacetic acid, 4,4′-Bipy = 4,4′-bipyridine, Phen = 1,10-phenanthroline, Mi = 1,4-bis(imidazol-1-yl)butane) have been synthesized and structurally characterized by single crystal X-ray diffraction (CIF files CCDC nos. 1047119 (I), 1047120 (II), 1047121 (III), 1047122 (IV)). The significant effect of assistant ligands and metal ions on assembly of I?IV has been demonstrated, which leads to the formation of distinct crystalline products. Complexes I?IV show various coordination motifs with different existing forms and coordination modes of the organic ligands. Furthermore, extend supramolecular networks are connected by secondary interactions such as hydrogen-bonding and aromatic stacking. The thermal stability and luminescent properties of the compounds were discussed in detail.  相似文献   

10.
Zinc(II) and manganese(II) complexes of 2-(diphenylacetyl)indandione-1,3 (HL) were synthesized. Crystals of [M(DMSO)2L2] · CHCl3, where M= Zn(II) (I) and Mn(II) (II), obtained from chloroform plus dimethyl sulfoxide (DMSO) mixture were found to be isostructural based on the similarity of their unit cell parameters and unit cell volumes. The crystals are triclinic, Z = 2, space group P \(\bar 1\); a = 10.422(1) Å, b = 11.929(1) Å, c = 20.429(1) Å, α = 73.616(1)°, β = 85.095(1)°, γ = 77.586(1)° for complex I; a = 10.436(1) Å, b = 12.297(1) Å, c = 19.924(2) Å, α = 78.138(2)°, β = 87.625(2)°, γ = 82.048(2)° for complex II. X-ray structural analysis of complex I was carried out. For complex II, the structure was not refined because all of its atoms are each disordered over three to five positions. The two DMSO molecules in complex I coordinate the central metal atoms in the monodentate mode via their donor oxygen atoms to occupy an axial position and an equatorial position in an octahedral polyhedron. The other four positions are occupied by the four oxygen atoms of the two deprotonated ligands L? coordinated in the bidentate-cyclic mode. The outer sphere of complex I contains the solvating chloroform molecule.  相似文献   

11.
Two new mononuclear Schiff base zinc(II) complexes, [ZnCl2(L1)] ? MeOH (I) and [Zn(L2)2] (II) (L1 = 2-bromo-4-chloro-6-[(2-ethylammonioethylimino)methyl]phenolate; L2 = 2-bromo-4-chloro-6-(isopropyliminomethyl)phenolate), have been prepared and characterized by elemental analyses, infrared and UV-Vis spectroscopy, and single-cyrstal X-ray diffraction (CIF files CCDC nos. 1408962 (I), 1408961 (II)). Complex I crystallizes in the triclinic space group \(P\overline 1\) with unit cell dimensions a = 9.859(1), b = 13.015(2), c = 19.817(3) Å, α = 73.591(2)°, β = 76.032(2)°, γ = 82.966(2)°, V = 2363.0(5) Å3, Z = 4, R 1 = 0.0925, and wR 2 = 0.2257. Complex II crystallizes in the monoclinic space group P21/c with unit cell dimensions a = 7.6387(7), b = 22.307(2), c = 21.443(2) Å, β = 96.216(3)°, V = 3632.4(6) Å3, Z = 8, R 1 = 0.0651, and wR 2 = 0.1100. The both Zn atoms in I is four-coordinated in a tetrahedral geometry by the NO donor set of the Schiff base ligand, and two Cl ligands. The Zn atom in II is in a tetrahedral geometry by two N and two O atoms from two Schiff base ligands. Crystals of the complexes are stabilized by hydrogen bonds and weak π…π interactions. Fluorescence property of the complexes have been determined.  相似文献   

12.
Bis(2-hydroxybenzaldehyde)-1,2-diaminoethane (LI), bis(2-hydroxybenzaldehyde)-1,3-diaminopropane (LII) and bis(2-hydroxybenzaldehyde)-4,4'-methylendianiline (LIII) were examined as ionophores for fabrication of polyvinylchloride (PVC) membrane Cu(II) ion-selective potentiometric sensors. The optimum composition (%) for the sensors was: 5 LI, 30 PVC, 6 sodium tetraphenylborate (NaTPB), 59 ortho-nitrophenyloctyl ether (NPOE); 4 LII, 30 PVC, 5 NaTPB, 61 dibutyl phthalate; 6 LIII, 30 PVC, 5 NaTPB, 59 NPOE. The linear response range of the electrodes was 5 × 10–4–0.05 (LI), 5 × 10–4–0.1 (LII) and 1 × 10–6–0.01 M (LIII), and the corresponding detection limits were 4 × 10–4, 4 × 10–4 and 2 × 10–7 M, respectively. The sensors were showed rapid response time (≈10 s). Their responses were independent on pH in the range 2.5–5.0 (LI), 3.2–4.7 (LII) and 4.0–5.0 (LIII). The selectivity of the prepared electrodes towards copper ions over some mono-, di- and trivalent metal ions was evaluated. The sensors were used as indicator electrode in potentiometric titration of copper ions in aqueous solutions.  相似文献   

13.
Coordination compounds [CoLCl2] (I), [CuLCl(NO3)] (II), CuL(NO3)2 (III), and CuLCl2 (IV) (where L is a chiral pyrazolylquinoline—a derivative of terpenoid (+)-3-carene) were synthesized. X-ray diffraction data showed that crystal structures I and II are built of mononuclear acentric molecules. In the molecule of complex I, the Co2+ ion coordinates two N atoms of bidentate cycle-forming ligand L and two Cl atoms. The coordination polyhedron of Cl2N2 is a distorted tetrahedron. For complex I, μeff = 4.50 μB, which corresponds to a high-spin configuration d 7. In the molecules of II(1), II(2) (which are diastereoisomers of complex II), each Cu2+ ion coordinates two N atoms of bidentate cycle-forming ligand L, the Cl atom, and two O atoms of bidentate cyclic NO 3 ? ion. The ClN2O2 coordination polyhedra are tetragonal pyramids with different degrees of distortion. The structure of complex II consists of supramolecular clusters, i.e., isolated chains incorporating the molecules of II(1) and II(2). The values of μeff for II–IV correspond to the d 9 configuration. The results of EPR and IR study suggest that complex III contains the O4N2 polyhedron, whereas complex IV contains the Cl2N2 polyhedron. Complexes I and IV were found to show a high catalytic activity in ethylene polymerization reaction.  相似文献   

14.
The complexes [CuLCl2] (I), [CoLCl2] (II), and CuLBr2 (III) (where L is the derivative of optically active 5-pyrazolone prepared from the terpene (+)-3-carene) were obtained and characterized. According to X-ray diffraction data, crystal structures I and II (orthorhombic crystal system) are built from mononuclear acentric molecules. In the resulting complexes, the Cu2+ or Co2+ ion coordinates two N atoms of the chelating bidentate ligand L and two Cl atoms, thus making a distorted tetrahedron. Intermolecular contacts and the hydrogen bonds Cl(1)…H-O(1) give rise to columns parallel to axis y. For complexes I and III, μeff = 1.83 and 1.81 μB, respectively; these values correspond to the electronic configuration d 9 . For complex II, μeff = 4.42 μB, which suggests the tetrahedral structure of the coordination entity CoCl2N2. Complexes I and III were studied by EPR spectroscopy.  相似文献   

15.
New cluster complexes of lanthanides(III) and nickel(II) [Ln{Ni(Gly)2}6]3+[Ln(NO3)6]3– have been synthesized, where Ln = La (I), Ce (II), and Pr (III); and Gly is glycinate. The structures of compounds IIII are determined by X-ray diffraction. The icosahedral cavity in the complex cation, where the lanthanide ion resides, has a fixed size independent of the nature of the central Ln(III) ion. In the complex anion, on the contrary, the Ln–O distances naturally decrease from La(III) to Pr(III). The optical properties of cationanion complexes IIII are studied. Based on the assignment in the electronic absorption spectra of the complexes, it is shown that the absorption bands are caused by d–d electronic transitions.  相似文献   

16.
Two new copper(II) complexes, [Cu(L1)2] (I) and [Cu(L2)2] (II), where L1 = 2-bromo-4-chloro- 6-(isopropyliminomethyl)phenolate and L2 = 2-bromo-4-chloro-6-[(2-hydroxyethylimino)methyl]phenolate, have been prepared and structurally characterized by X-ray crystallography (CIF files CCDC nos. 1445936 (I) and 1445935 (II)). In both complexes, the Cu atoms are coordinated by two phenolate oxygen and two imino nitrogen, giving square planar geometry. The complexes have been tested on various strains of bacteria to study their antibacterial effects.  相似文献   

17.
The NiCl2 and CoCl2 complexes with 4,5-(2-pyridylethylene)-dithio-1,3-dithiol-2-thione (L1) and 4,5-(4-pyridylethylene)-dithio-1,3-dithiol-2-thione (L2) were described. The L1 ligand shows bidentate coordination through the pyridyl N atoms and the thiol S atoms in a tetrahedral [CoCl2(L1)] complex (I) and in an octahedral [NiCl2(L1)2](MeCN)2 complex (II). The L2 ligand exhibits monodentate coordination through the pyridyl N atom in tetrahedral complexes [CoCl2(L2)2 (III) and [NiCl2(L2)2] (IV). Complexes I, III, IV in crystal state are octahedral due to extra coordination of the thione S atoms or the chloride bridges responsible for the polymeric structure. The structure of the complex II · CH2Cl2 was determined by X-ray diffraction analysis. The crystals are monoclinic, space group P21/c, a = 11.895(2) Å, b = 13.374(3) Å, c = 21.873(4) Å, β = 95.30(3)°, Z = 2. The Ni atom has quasi-tetrahedral surrounding due to two chloride ions and two L1 ligands coordinated through the pyridyl N atoms and the thiol S atoms.  相似文献   

18.
Two new 1,3-bi(4-pyridyl)propane-based cadmium(II) complexes, [Cd(Bpp)2(Nas)2] n (I) and [Cd(Bpp)2(Na)2(H2O)2] (II) (Bpp = 1,3-bi(4-pyridyl)propane, Nas = 2-aminonaphthalene-1-sulfonate, and Na = 1-naphthoate) (CIF files CCDC nos. 1429589 (I), 1429590 (II)) have been hydrothermally synthesized by varying carboxylate- or sulfonate-containing coligands. Structural analyses reveal that, complex I with monodentate Nas ligands exhibits a two-dimensional (2D) layered motif extended by equatorial Bpp connectors. By contrast, complex II modified by monodentate Na ligands exhibit discrete mononuclear structure. Althouth the Nas/Na coligands showed the same monodentate binding modes, the Bpp ligand exhibits bridging or terminal binding modes in I and II, respectively. So it is obvious that the competitive coordination in the present mixed-ligands system is responsible for the aggregation or dissociation of mononuclear structural units. Furthermore, both of the two compounds are linked to 3D supramolecular architecture by intermolecular C–H···O hydrogen bonding or C–H···π stacking interactions, exhibiting strong fluorescent emissions resulting from the ligand-to-metal or Na?-based intraligand charge transfer at room temperature, which can be hopefully used as fluorescent materials.  相似文献   

19.
The phenolic azide bridged dinuclear nickel(II) complex, [Ni2(L1)2(N3)(H2O)(μ1,1-N3)] · EtOH (I), and the thiocyanate bridged dinuclear copper(II) complex, [Cu2(L2)21,1-NCS)2] (II), where L1 and L2 are the deprotonated forms of 2-mothoxy-6-[(2-piperidin-1-ylethylimino)methyl]phenol and 2,4-dichloro-6-[(2-methylaminoethylimino)methyl]phenol, respectively, were synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. The crystal of I is orthorhombic: space group Pbca, a = 12.172(1), b = 20.953(1), c = 29.779(2) Å, V = 7594.8(9) Å3, Z = 8. The crystal of II is monoclinic: space group P21/n, a = 8.7615(11), b = 19.672(2), c = 16.568(2) Å, β = 99.449(2)°, V = 2816.9(6) Å3, Z = 4. The Ni atoms in I are in octahedral coordinations, and the Cu atoms in II are in square-pyramidal coordinations.  相似文献   

20.
Reaction of tridentate Schiff bases with nickel and cadmium salts in methanol afforded two new mononuclear complexes, [Ni(L1)2] (I) and [Cd(L2)2] (II), where L1 and L2 are the anions of 2-bromo-4-chloro-6-[(3-dimethylaminopropylimino)methyl]phenol (HL1) and 2-bromo-4-chloro-6-[(3-morpholin-4-ylpropylimino)methyl]phenol (HL2), respectively. The complexes were characterized by singlecrystal X-ray diffraction (CIF files CCDC nos. 1428653 (I) and 1428654 for (II)), FT-IR, and elemental analysis. Complex I crystallizes in the monoclinic space group P2 1/c, with a = 8.8216(8), b = 14.0424(8), c = 11.8687(12) Å, β = 111.238(2)°, V = 1370.4(2) Å3, Z = 2. Complex II crystallizes in the monoclinic space group P2 1/n, with a = 9.6774(4), b = 15.8970(6), c = 20.3144(7) Å, β = 90.408(2)°, V = 3125.1(2) Å3, Z = 4. The metal atoms in the complexes are coordinated by two tridentate Schiff base ligands, forming octahedral coordination. The free Schiff bases and the complexes were assayed for antibacterial activities. Both complexes are more active against the bacteria than the free Schiff bases. Complex II has the MIC value of 0.39 μg mL–1 against Bacillus subtilis.  相似文献   

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