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1.
Three new copper(II) complexes with isonicotinic acid N-oxide (HL) and 1,10-phenanthroline (phen) as ligands, [Cu(L)(phen)(H2O)]2(NO3)2···2H2O (1), [Cu(L)(phen)(H2O)]2(ClO4)2···2H2O (2), and [Cu(L)(phen)Br]2- [Cu(L)(phen)(H2O)]2Br2···6H2O (3) have been synthesized and structurally characterized. The structures of all three complexes feature a Cu2 dimer formed by two Cu(II) ions interconnected by two bridging ligands. Each copper(II) ion has a distorted square pyramidal coordination geometry with elongated axial coordination by an aqua ligand or halogen anion. The isonicotinic acid N-oxide anion is bidentate, being coordinated to two Cu(II) ions through its N-O oxygen and one of its carboxylate oxygen atoms. Magnetic susceptibility measurements show a Curie–Weiss paramagnetic behavior characteristic of one unpaired electron for a copper(II) ion for all three complexes.  相似文献   

2.
2-(2-Pyridyl)benzimidazole (PBI) was synthesized by solvent-free aldol condensation and complexed with nickel(II) and copper(II) nitrate and perchlorate salts by simple reactions at room temperature. The transition metal complexes [Ni(PBI)2NO3](NO3) (1), [Ni(PBI)3](ClO4)2·1.5H2O (2), [Cu(PBI)2NO3](NO3) (3), and [Cu(PBI)3](ClO4)2·3H2O (4) (PBI = 2-(2-pyridyl)benzimidazole) were synthesized in good yield and structurally characterized by X-ray crystallography, infrared absorption spectroscopy, and elemental analysis. Complexes 1 and 3 are isostructural, crystallizing in the same space group P21/c. Both the nickel(II) and copper(II) atoms have distorted square pyramidal geometries. The metal centers in these complexes are coordinated by two molecules of the bidentate ligand (PBI) and an O-atom of the coordinated nitrate anion. Complexes 2 and 4 are also isostructural but do not crystallize in the same space group: P-1 for 2 and Pccn for 4. The geometry around both the nickel(II) and the copper(II) centers is distorted octahedral. Here, the metal atoms are coordinated by three molecules of 2-(2-pyridyl)benzimidazole. The copper(II) complex 4 has 2-fold symmetry with one of the three PBI ligands being positionally disordered about the 2-fold axis. Intermolecular N–H···O hydrogen bonds, involving the NH H-atom and an O-atom of the coordinated nitrate anion, are observed in all four complexes. In 1 and 3, this gives rise to the formation of centrosymmetric dimer-like structures that are decorated by hydrogen-bonded nitrate anions. In 2 and 4 the perchlorate anions and the water molecules of crystallization are involved in N–H···O and O–H···O hydrogen bonds bridging two symmetry-related cations, thus forming cyclic arrangements. In the case of complex 4, this leads to the formation of two-dimensional hydrogen-bonded networks parallel to plane (011). Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

3.
Copper(II) complexes of 3-methylpicolinic acid (3-MepicH), namely [Cu(3-Mepic)2] · 2H2O (1) and [Cu(3-Mepic)2(4-pic)] (2) were prepared and characterized by IR spectroscopy and thermal analysis (TGA/DTA). Crystal structure for 2 was determined by X-ray crystal structure analysis. 1 was prepared by reaction of copper(II) sulfate pentahydrate and 3-methylpicolinic acid in aqueous solution, while 2 was prepared by recrystallization of 1 from 4-picoline solution. Structure analysis revealed square-pyramidal copper(II) coordination and N,O-chelating mode of 3-methylpicolinic acid in 2. Copper(II) is coordinated by two 3-Mepic ligands in the basal plane of a square pyramid and by 4-picoline in the apical position. Crystal packing of 2 is dominated by weak intermolecular C–H ··· O hydrogen bonds and π ··· π stacking interactions forming a complex three-dimensional supramolecular architecture.  相似文献   

4.
A copper(II) complex [Cu(im2-py)(4,4′-bipy)(NO3)](NO3)·1.5H2O (im2-py?=?2-(2′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl; 4,4′-bipy?=?4,4′-bipyridyl) has been synthesized by reaction of Cu(NO3)·3H2O with im2py and 4,4-bipyridyl in methanol solution. Its crystal structure has been determined by X-ray diffraction. The structure shows that each copper ion is coordinated by a bidentate imino nitroxide radical, two 4,4′-bipyridyl ligands and a nitrate group to form a distorted square pyramidal environment. The crystal structure consists of chains of copper ions linked by 4,4′-bipyridyl.  相似文献   

5.

The title complex [Cu2(C4H2O4)2(bipy)2(H2O)3] · 3H2O (bipy = 2,2'-bipyridine) was prepared and its crystal structure determined by X-ray diffraction methods. Both Cu(II) atoms of the binuclear complex assume square pyramidal coordination. The fumarate groups display different coordination modes. One fumarate group bridges two Cu(II) ions to form a binuclear complex while another fumarate group terminally coordinates to a Cu(II) atom with one carboxyl group free from coordination. The terminally coordinated fumarate showed unusual disorder, which may be due to an intermolecular H-bonding interaction. Close stacking of bipy rings is observed as verified by the distance of 3.46 Å between parallel ring planes. IR spectra were assigned based on the molecular structure.  相似文献   

6.
A novel monomer copper(II) complex [Cu(L)2(SCN)] · ClO4 (1) and a tetranuclear cobalt(II) complex [Co4(L)4(N3)4](OH)4 · 2H2O (2)(L = 3,6-bis-(3,5-dimethylpyrazolyl)-pyridazine) have been synthesized and structurally characterized. Single crystal X-ray analyses show that the Cu(II) atom is in a distorted trigonal bipyramidal coordinated environment consisting of four N atoms of L and one N atom of SCN in complex (1), and the monomer is extended to a 1D chain by the weak intermolecular π...π stacking interactions. In the complex (2), four Co(II) atoms are linked by four bridging azido groups in μ-1,1-N3 (end-on) coordination mode to form a tetranuclear configuration. The fungicidal activity of the title compounds have been studied, and the results show that there are certain activities against several bacteria for the complexes and the ligand. Furthermore, two complexes exhibit blue emission fluoresce in the solid state at room temperature.  相似文献   

7.
A cobalt(II) compound, [Co4(L)2(OH)2(phen)2(H2O)4] · 6H2O (1), and a copper(II) compound, [Cu2(L)2(H2O)2][Cu(H2O)6] · 6H2O (2) [where H3L is 2-hydroxy-3-[(2-sulfoethylimino)-methyl]-benzoic acid and phen is O-phenanthroline], were prepared and characterized. The tetranuclear cobalt complex 1, C44H62N6O28S2Co4, crystallizes in the monoclinic space group P21/c, with a = 11.847(10) Å, b = 19.061(15) Å, c = 12.635(10) Å, β = 105.483(9)°, and Z = 2; R 1 for 4821 observed reflections [I > 2σ(I)] was 0.0679. Complex 1 is a centrosymmetric tetranuclear cobalt complex with all cobalts having distorted octahedral geometry. The molecule can be viewed as two planar [Co2(OH)(L)(Phen)H2O] units tied together by two terminal water molecules. The framework of 1 has the appearance of two connected face-sharing cubes, each with one vertex missing. The trinuclear copper complex 2, C20H44Cu3N2O26S2, crystallizes in the triclinic space group P1, with a = 7.524(1) Å, b = 7.902(2) Å, c = 16.885(4) Å, α = 88.993(6)°, β = 80.725(7)°, γ = 66.725(4)° and Z = 1; R 1 for 4298 observed reflections [I > 2σ (I)] was 0.0360. Complex 2 is an ionic compound, in which the three Cu(II) centers have two coordination modes. The molecule has a centrosymmetric dinuclear copper coordinated anion and a hexa-aqua-copper cation. The sulfonic acid group has less coordination ability than carboxylate oxygen.  相似文献   

8.
New complexes of Co(II), Ni(II), and Cu(II) nitrates, chlorides, and perchlorates with 4-(4-hydroxyphenyl)-1,2,4-triazole (L) were obtained and examined by single-crystal X-ray diffraction, X-ray powder diffraction, and electronic absorption and IR spectroscopy. The cations of all the complexes have linear trinuclear structures. Ligand L is coordinated to the metal ions in a bidentate bridging fashion through the N(1) and N(2) atoms of the heterocycle. The coordination polyhedron of the metal atoms is a distorted octahedron. The molecular and crystal structures of the complexes [Co3L6(H2O)6](ClO4)6 · 3C2H5OH · 3.75H2O and [M3L6(H2O)6](ClO4)6 · 6H2O (M = Cu2+ and Ni2+) were determined.  相似文献   

9.
Three new complexes, [Cu(barb)2(aepip)] · 0.5H2O (1), [Cu(barb)2(aepyrd)] (2), and [Cu(barb)2(aemrph)] (3), have been synthesized by reaction of 5,5-diethlybarbiturate anion (barb) with copper(II) in the presence of (2-aminoethyl)piperidine (aepip), -pyrrolidine (aepyrd), and -morpholine (aemrph). All complexes were characterized by elemental analysis, spectroscopic (IR and UV/Vis), thermal (DTA-TGA), and magnetic susceptibility measurements. X-ray single crystal diffraction shows that 1 and 2 are discrete mononuclear species, in which copper(II) is coordinated by two bidentate barb ligands and a chelating aepip or aepyrd, forming a square-pyramidal coordination geometry. Complexes 1 and 2 show unequal coordination of barb, one N-coordinate, and one bidentate. Complex 3 is also mononuclear, but copper(II) is square-planar with two N-coordinated barb and one bidentate aemorph. Molecules of 13 are bridged by strong hydrogen bonds to generate 1-D or 2-D supramolecular networks. Spectral and thermal data for 13 are in agreement with crystal structures.  相似文献   

10.
Three new mononuclear complexes [Co(2-Acpy)2(H2O)2](NO3)2 (1), [Ni(2-Acpy)2(H2O)2](NO3)2 (2) and [Cd(2-Acpy)2(NO3)2] (3) (2-Acpy = 2-acetylpyridine) have been synthesized and characterized by elemental analysis, IR and UV–Vis spectroscopy. The structures of 1 and 3 were accomplished by single crystal X-ray diffraction. Crystallographic investigation of 1 reveals monomeric, dicationic units in which the cobalt(II) ion is six-coordinate. The coordination sphere is formed by two N, O bidentate acetylpyridine ligands and two water molecules. The crystal structure of 3 consists of monomeric units in which the cadmium is eight-coordinate. Both the organic ligand and nitrate groups are bidentate chelators. The supramolecular solid-state architecture is sustained by π–π interactions.  相似文献   

11.
Three new zinc(II) complexes, Zn(L1)(NO3)2 (1), {[Zn(L1)(fumarate)]·2H2O} n (2) and {[Zn(L2)(fumarate)]·DMF} n (3) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,01.18,07.12]docosane) have been synthesized and characterized by analytical, spectroscopic, thermal and X-ray diffraction methods. The structure of the discrete neutral complex (1) shows that the central zinc(II) ion is coordinated axially by two nitrate ligands. In the structures (2) and (3), the carboxylate groups of the bridging fumarate ligands are coordinated to zinc(II) macrocycles, resulting in the formation of 1D coordination polymers. Apart from the fairly strong Zn–O bonds in (2) and (3), it is observed that the hydrogen bonds between the pre-organized N–H groups of the macrocycle and axial ligands appear to be important for the design and development of metal complexes having a strong Zn–O bond.  相似文献   

12.
Four new nickel(II), zinc(II), and cobalt(II) complexes, [Zn(L1)2]?·?H2O (1), [Ni(L1)2]?·?H2O (2), [Ni(L2)2] (3), and [Co(L3)2]?·?H2O (4), derived from hydroxy-rich Schiff bases 2-{[1-(5-chloro-2-hydroxyphenyl)methylidene]amino}-2-methylpropane-1,3-diol (HL1), 2-{[1-(2-hydroxy-3-methoxyphenyl)methylidene]amino}-2-ethylpropane-1,3-diol (HL2), and 2-{[1-(5-bromo-2-hydroxyphenyl)methylidene]amino}-2-methylpropane-1,3-diol (HL3) have been synthesized and characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray determination. Each metal in the complexes is six-coordinate in a distorted octahedral coordination. The Schiff bases coordinate to the metal atoms through the imino N, phenolate O, and one hydroxyl O. In the crystal structures of HL1 and the complexes, molecules are linked through intermolecular O–H···O hydrogen bonds, forming 1-D chains. The urease inhibitory activities of the compounds were evaluated and molecular docking study of the compounds with the Helicobacter pylori urease was performed.  相似文献   

13.
Anodic oxidation of cobalt and copper metals in an anhydrous acetone solution of pyridine-2-(1H)-thione-3-cyano-4-(2-bromophenyl)-5,6-ring fused cycloheptane (HL1) and its derivatives, (HL2), (HL3), (HL4), (HL5), (HL6), (HL7), (HL8), and (HL9) yields complexes of composition [M(L)2·(H2O)2]·n H2O and [M(L)2·(acetone)2], where M = Co(II) or Cu(II) and L is the ligand. Also, reaction of an aqueous ethanolic solution of Co(Ac)2·2H2O with the previous ligands was prepared. Elemental analysis, and infrared and electronic spectral data are presented to confirm the formulation of the amorphous complexes. The spectral data indicate that the ligands are coordinated to the metal via the thioenol sulfur atom and the nitrogen atom of cyano groups. The ligands reacts in the enol form through the anodic dissolution of the ligands or during the reaction with metal salts. The ligand field parameters and crystal field splitting energies, Δo, for different cobalt metal complexes were calculated.  相似文献   

14.
The crystal structures of three copper(II) complexes of pyridine-2,6-dithiocarbomethylamide (P DT A) were determined by X-ray crystallographic methods. The structure of the bromide CuP DT ABr2 · H2O (2) is isomorphous to the known crystal structure of the chloride CuP DT ACl2 · H2O (1). The iodide CuP DT AI2 ·D M F (3) is non-isomorphous to the other two halogenides, but shows a very similar square-pyramidal 5-coordination of the copper atom. In contrast to the halogenides, the crystal structure of the nitrate CuP DT A (H2O)2 · (NO3)2 (4) shows a square planar metal coordination by theP DT A ligand and one water molecule. If one includes the second water molecule and one oxygen atom of a nitrate ion, the metal coordination becomes distorted octahedral.  相似文献   

15.
Two new transition metal dicyanamide complexes [Co2(tppz)(dca)4]·CH3CN ( 1 ) [tppz=tetra(2‐pyridyl)pyrazine, dca=dicyanamide] and [Co(tptz)(dca)(H2O)](dca) ( 2 ) [tptz=2,4,6‐tri(2‐pyridyl)‐1,3,5‐triazine] were synthesized and characterized by single crystal X‐ray diffraction analysis. In 1 each cobalt(II) atom is coordinated to three dca anions and one tppz molecule to form a distorted octahedral geometry, the neigbour two cobalt(II) atoms are bridged by one tppz ligand to form a dimer, then the cobalt(II) atoms in each dimer are joined together to form a ladder chain structure. In 2 the coordination geometry around the central metal is also distorted octahedral, each cobalt(II) atom is coordinated by two dca anions, one tptz molecule and one water ligand to form a cationic part, and the cationic part is linked with the free dca anions via the electrostatic attraction to give an infinite chain structure. Magnetic susceptibility measurement in the range of 2–300 K indicates that there are antiferromagnetic couplings between adjacent metal ions in 1 (T>29 K, (=?9.78 K, C=4.92 cm3·K·mol?1) and ferromagnetic couplings in 2 (T>150 K, (=7.97 K, C=2.59 cm3·K·mol?1) respectively.  相似文献   

16.
Two cadmium(II) and two zinc(II) coordination complexes with diverse structural motifs, [Cd2(HL)I3H2O] · H2O ( 1 ), [Cd2(H2L)2(H2O)4] · 2SO4 · 14H2O ( 2 ), [Zn3(L′)2(H2O)6] · 4H2O · 2(NO3) ( 3 ), and [Zn3L'2(H2O)2Cl2] · H2O ( 4 ) [H2L = 1,1‐bis(5‐(pyrid‐2‐yl)‐1,2,4‐triazol‐3‐yl)methane; H2L′ = 1,1‐bis(5‐(pyrid‐2‐yl)‐1,2,4‐triazol‐3‐yl)methanone] were synthesized through a hydrothermal method. These coordination complexes were characterized by single‐crystal X‐ray diffraction, powder X‐ray diffraction (PXRD), FT‐IR spectroscopy, and photo‐luminescent experiments. Single crystal structural analysis revealed that 1 – 4 belong to polynuclear coordination compounds. PXRD analysis of 1 – 4 unambiguously confirmed the purity of the as‐synthesized coordination compounds. It is the first time to synthesize coordination compounds based on H2L′, which reacted from the original material H2L through in‐situ hydrothermal conditions. In addition, photo‐luminescent experiments revealed that 1 – 4 have real‐time sensing effects for benzaldehyde through fluorescence quenching. For 1 – 4 , the photo‐luminescent quenching effect for benzaldehyde was also compared and the coordination complexes 3 and 4 based on H2L′ have higher photo‐luminescent quenching effect than compounds 1 and 2 .  相似文献   

17.
Four new substituted amino acid ligands, N-(3-hydroxybenzyl)-glycine acid (HL1), N-(3-hydroxybenzyl)-alanine acid (HL2), N-(3-hydroxybenzyl)-phenylalanine acid (HL3), and N-(3-hydroxybenzyl)-leucine acid (HL4), were synthesized and characterized on the basis of 1H NMR, IR, ESI-MS, and elemental analyses. The crystal structures of their copper(II) complexes [Cu(L1)2]·2H2O (1), [Cu(L2)2(H2O)] (2), [Cu(L3)2(CH3OH)] (3), and [Cu(L4)2(H2O)]·H2O (4) were determined by X-ray diffraction analysis. The ligands coordinate with copper(II) through secondary amine and carboxylate in all complexes. In 2, 3, and 4, additional water or methanol coordinates, completing a distorted tetragonal pyramidal coordination geometry around copper. Fluorescence titration spectra, electronic absorption titration spectra, and EB displacement indicate that all the complexes bind to CT-DNA. Intrinsic binding constants of the copper(II) complexes with CT-DNA are 1.32?×?106?M?1, 4.32?×?105?M?1, 5.00?×?105?M?1, and 5.70?×?104?M?1 for 1, 2, 3, and 4, respectively. Antioxidant activities of the compounds have been investigated by spectrophotometric measurements. The results show that the Cu(II) complexes have similar superoxide dismutase activity to that of native Cu, Zn-SOD.  相似文献   

18.
Two new coordination polymers, {[Eu2(L1)3(H2O)2]?·?H2O} n (1), (Cu(II)?···?Cu(II), [Tb(H2O)]2(L2)3?·?4H2O (2) (H2L1?=?succinic acid, H2L2?=?glutaric acid) have been hydrothermally synthesized and characterized by elemental analysis, IR, luminescence spectra and single crystal X-ray diffraction. The complexes are constructed by dicarboxylates bridging chains of edge-sharing EuO8(H2O) and TbO8(H2O) polyhedra to form 3D network structures. Complexes 1 and 2 exhibit intense red and green photoluminescence upon UV excitation in the solid state at room temperature.  相似文献   

19.
Abstract

The compounds [Cu(oxpn)] (1), [(bpy)(H2O)Cu(μ-cis-oxpn)Cu(H2O)] · 2NO3 · 2H2O (2) and [(Him)(NO3)Cu(μ-trans-oxpn)Cu(Him)(NO3)] (3), where oxpn is the dianion of N,N′-bis(3-aminopropyl)oxamide, bpy is bipyridine and Him is imidazole, were prepared and characterized by elemental analysis and IR spectra. Complex (2) was also studied by thermochemical analysis and its structure determined by X-ray crystallography. The structure of complex (2) consists of binuclear copper(II) molecules in which the copper(II) atoms are bridged by an oxamidato group in the cis conformation resulting a copper-copper distance of 5.21 Å. Both copper(II) ions are in square-pyramidal surroundings with almost coplanar basal planes and a water molecule occupying the apical positions. The N atoms of the oxamidato moiety are trigonal. Two lattice water molecules together with the two coordinated ones hydrogen bond with nitrate ions.  相似文献   

20.
《Polyhedron》2001,20(9-10):1079-1087
The crystal and molecular structure of sodium 5-sulfosalicylate dihydrate, Na[(H2Ssal)(H2O)2], (1) (H3Ssal=5-sulfosalicylic acid) has been determined through X-ray diffraction analysis. The 5-sulfosalicylate anion has lost the proton at the SO3H group but retains the usual intermolecular hydrogen bond between phenolic and carboxylic oxygen. The reaction in water of 1 with [Cu(II)(H2O)4]SO4·H2O, gives rise to the green sodium[triaqua(5-sulfosalicylato)copper(II)] 2 hemihydrate, Na[(H2O)3(Ssal)Cu(II)]·2×0.5H2O, (2). The 5-sulfosalicylate anion, (Ssal3−), coordinates rather unusually in the synsyn coordination mode since it binds bidentately the Cu(II) ion through the carboxylic and the phenolic oxygens, with Cu(II)Ocarboxylic=1.909(4) Å and Cu(II)Ophenolic=1.885(4) Å distances. Copper(II) completes its square-planar coordination with two water molecules and in addition, perpendicularly to the square-planar coordination plane, another two water molecules with long bonds are present (Cu(II)O=2.518 and 2.912 Å). The green complex 2 reacts easily with adenine in water at pH 7 giving rise to the violet tetraadeninato(diaqua)-bis(copper(II)) dihydrate, [Cu2(Ade)4(H2O)2])]·2H2O, (3) (Ade=adeninato monoanion). This complex, that geometrically resembles copper(II) acetate monohydrate, was already described by Sletten. Finally, on the basis of the present results a possible mechanism for the anticancer activity of complex 2 and of other Cu(II)–salicylate complexes is proposed and discussed.  相似文献   

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