Synthesis,spectral studies,thermal behavior,and antibacterial activity of Ni(Ⅱ),Cu(Ⅱ),and Zn(Ⅱ) complexes with an ONO tridentate Schiff base

Three new transition metal complexes have been synthesized with a Schiff base,3-(2-hydroxy-5-chlorophenylimino)-l,3- diphenylpropen-1-one.In all complexes Schiff base is completely deprotonated and coordinated to metal as tridentate ligand via phenolic and enolic oxygens and imine nitrogen.Thermal decomposition of the complexes has been studied by thermogravimetry. The in vitro antibacterial activity of Schiff bases and their complexes has been evaluated and compared with the standard drugs.     

A Novel Cobalt（Ⅲ） Complex with Macrocyclic Triamine Ligand for High Capacity Hydrogen Adsorption

The coordination complex of Co(Ⅲ) based on a macrocyclic triamine ligand 1,4-diacetate-1,4,7-triazacyclodecane (L) has been synthesized and characterized. The metal cation is bonded with three nitrogen atoms and two oxygen atoms of L and one chloride ion to form a distorted octahedral geometry. This complex coordinated with macrocyclic ligand possesses large pore volume that will be contributed to observe high H2 adsorption. With respect to the first-principles electronic structure calculations, the feasibility to store hydrogen in the complex is explored. Indeed, the complex has shown a very high total H2 adsorption of 7.2 wt% (wt% = (weight of adsorbed H2)/(weight of host material)), with a binding energy of 0.03 eV/H2.     

Syntheses, Crystal Structures and Photoluminescence Properties of Cadmium(Ⅱ) and Nickel(Ⅱ) Complexes with 2-(2-Benzimidazolyl)quinoline

Two novel complexes, [Cd2(BMQU)2Cl4] (1) and [Ni(BMQU)2HPO4]·1.5H2O (2) (BMQU = 2-(2-benzimidazolyl)quinoline), were synthesized by the hydrothermal method and characterized by elemental analysis, IR, and TG-DTG. The crystal structures were determined by single-crystal X-ray diffraction. Both 1 and 2 crystallize in the triclinic system, space group P . The data for 1: a = 0.8342(7), b = 0.9226(9), c = 1.0646(8) nm, α = 90.819(2), β = 97.466(2), γ = 98.280(2)°. The Cd(Ⅱ) is coordinated with three chlorine atoms and two nitrogen atoms of a BMQU molecule, generating a distorted square-pyramidal geometry. The dinuclear Cd(Ⅱ) complex is formed by two chlorine bridge bonds, and the one-dimensional chain structure is constructed with the hydrogen bond N-H…Cl and π-π stacking interaction. The data for 2: a = 1.2251(1), b = 1.2451(1), c = 1.2868(1) nm, α = 107.510(2), β = 98.630(1), γ = 109.921(2)°. The Ni(Ⅱ) is coordinated with four nitrogen atoms of two BMQU molecules and two oxygen atoms of a HPO42-, forming a distorted-octahedral geometry. The two-dimensional layer structure is formed by the hydrogen bonds and π-π stacking interaction between neighboring molecules. Complex 1 shows a strong blue fluorescence emission (λmax= 456 nm) at solid state.     

PMBP缩1-萘胺合钴(Ⅱ)配合物的合成和晶体结构

Using 4-[(1-naphthylamino)phenylmethylene]-5-methyl-2-phenyl-2H-pyrazol-3(4H) one (L), its Co(Ⅱ) complex was synthesized and characterized by IR and UV in which the ligand as a -1 valence bidentate with Co(Ⅱ) form 2∶1 complex. X-ray structure analysis indicates that the Co(Ⅱ) ion is coordinated with oxygen atoms of pyrazolinon, nitrogen atoms of imine and oxygen atoms of DMF molecules to form a distorted six-coordination octahedron. π-π reciprocity and aromatic stack interaction are observed. There are no intra- and inter- hydrogen bond in the crystal and the complexes are held together by electronic and Van der Waals forces.     

Synthesis and Crystal Structure of [Ni(bdpm)_2(OAc)]_2(N_3)_2·5H_2O(bdpm=Bis(3,5-dimethylpyrazol-1-yl)methane,OAc=CH_3COO~-)

1 INTRODUCTION Bis(pyrazol-1-yl)methane has been one of the po- pular polydentate nitrogen donor ligands due to its strong chelating coordination to transition metal ions as capping ligand. Coordination behavior of the li- gand is able to yield stable M-N-N-C-N-N six-mem- bered boat conformation[1, 2]. The complexes con- taining bdpm ligand have been widely synthesized and characterized in recent years, and exhibit the striking properties in catalysis, magnetism and so on[3-10]. For exa…     

Synthesis and Crystal Structure of [Cu(acac)(Hdmpz)_3]Br.EtOH

1 INTRODUCTION Diazoles have both a pyridine-type nitrogen and a pyrrole-type nitrogen (imino group), so they can act as bifunctional groups to coordinate with many metal ions or Lewis acids giving a variety of products[1, 2]. Recently researches on the pyrazole ligand have been focused on the following three sections. (i) The first is that the ligand acts as a bridged ligand and coordinates to metal forming di- and polynuclear complexes. Such system arouses much interest mainly because o…     

Synthesis,Crystal Structure and Physical Properties of a Novel Cadmium(Ⅱ) Supramolecular 3D Framework

A new inorganic-organic hybrid cadmium(Ⅱ) complex [Cd2(H1/2C4BIm)2(CH3COO)]nhas been prepared by a hydrothermal reaction,and characterized by fluorescence,IR,TGA,and single-crystal X-ray diffraction analysis.In its crystal structure,there are two kinds of coordinating forms for those Cd(Ⅱ) ions.One is that the Cd(Ⅱ) ion is coordinated by one carboxylate oxygen atom from one acetate oxygen ligand and three benzimidazole nitrogen atoms from three 2,2’-(1,4-butanediyl)bis(1H-benzimidazole)(H2C4BIm) ligands,and the other is that the Cd(Ⅱ) ion is coordinated by four benzimidazole nitrogen atoms from four H2C4 BIm ligands to furnish two distorted tetrahedral coordination geometries.It exhibits a beautiful structure for a 2D layer and a 3D network,with its four-connecting nodes provided by the H2C4 BIm ligands.Furthermore,this complex shows intense luminescent property at room temperature.In [Cd2(H2C2BIm)2(C9H6O4)2]n,the H2C2 BIm ligand lost the role as a bridging ligand because of the shorter alkyl chain compared with that of H2C4 BIm ligand.     

Synthesis and Crystal Structure of a Novel Co(II)-Nitronyl Complex [Co(IM2-Py)(PCA)(N_3)_2]

1 INTRODUCTION The design and synthesis of molecule-based mag-netic materials is one of the major subjects of mate-rials science. Nitronyl nitroxides acting as useful pa-ramagnetic building blocks have been extensively usedto assemble molecular magnetic materials in the pastfew years[1～5]. However, their weakly basic charac-ter strongly limits their coordination ability. Mean-while, the azide anion is a versatile ligand which canlink the transition metal atoms with different coor-dinatio…     

Synthesis and Crystal Structure of a One-dimensional Azido-bridged Manganese (II) Compound [Mn(N_3)_2(H_2O)_3·C_6H_(12)N_4]_n

1 INTRODUCTION The azide anion is a good bridging ligand for di- valent metal ions to form discrete, one-dimensional, two-dimensional or three-dimensional complexes. In recent years, these complexes have drawn consider- able attentions for their interesting magnetic charace- ristics which attribute to the efficient magnetic coup- ling ability of the azido bridges[1]. When the azide anion acts as a bridging ligand, two typical modes are adopted: end-to-end (EE, μ1, 3) or end-on (EO, μ1…     

Four Complexes of Mn(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Cu(Ⅱ) Based on 2-Morpholine-4-yl-4,6-di-pyrazol-1-yl-1,3,5-triazine

Three azide bridged complexes, namely, [Mn_2L_2(N_3)_4(H_2O)_2](1), [Co_2L_2(N_3)_4]·(H_2O)_3(2) and [Ni_2L_2(N_3)_3(H_2O)]N_3·(H_2O)_4(3)(L = 2-morpholine-4-yl-4,6-di-pyrazol-1-yl-1,3,5-triazine), were synthesized by the reaction of L ligand, sodium azide with Mn(Ⅱ), Co(Ⅱ) and Ni(Ⅱ) chlorides. The copper(Ⅱ) chloride combined with thiocyanate and L ligand to form a mononuclear complex [CuL(CH_3OH)(SCN)(NCS)](4). Complexes 1~4 were characterized by IR, elemental analysis and X-ray crystallographic analysis. It was worth noting that two Mn(Ⅱ) atoms were connected by the end-to-end mode in 1, while Co(Ⅱ) and Ni(Ⅱ) atoms were connected by the end-on mode in 2 and 3. In complex 4, the central copper atom was coordinated with a sulfur atom and a nitrogen atom of the two thiocyanate ligands, respectively. Hydrogen bonds, π-π stacking interactions, thermogravimetric analysis and fluorescence properties of 1~4 were studied.     

[Bis(3,5‐dimethylpyrazol‐1‐yl‐κN2)dithioacetato‐κS](triphenylphosphine‐κP)copper(I)

In the title compound, [Cu(C₁₂H₁₅N₄S₂)(C₁₈H₁₅P)], the copper(I) center is tetrahedrally coordinated by one S atom and two N atoms from one bis(3,5‐dimethylpyrazol‐1‐yl)dithioacetate ligand and one P atom from a triphenylphosphine ligand. In the crystal structure, adjacent pyrazole rings are involved in weak π–π interactions, thereby forming a one‐dimensional zigzag chain running along the b axis.     

In situ synthesis of mononuclear copper(II) complexes of the new tridentate ligand bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methyl]amine

Two mononuclear copper complexes, {bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl‐κN²)methyl]amine‐κN}(3,5‐dimethyl‐1H‐pyrazole‐κN²)(perchlorato‐κO)copper(II) perchlorate, [Cu(ClO₄)(C₅H₈N₂)(C₁₂H₁₉N₅)]ClO₄, (I), and {bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl‐κN²)methyl]amine‐κN}bis(3,5‐dimethyl‐1H‐pyrazole‐κN²)copper(II) bis(hexafluoridophosphate), [Cu(C₅H₈N₂)₂(C₁₂H₁₉N₅)](PF₆)₂, (II), have been synthesized by the reactions of different copper salts with the tripodal ligand tris[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methyl]amine (TDPA) in acetone–water solutions at room temperature. Single‐crystal X‐ray diffraction analysis revealed that they contain the new tridentate ligand bis[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methyl]amine (BDPA), which cannot be obtained by normal organic reactions and has thus been captured in the solid state by in situ synthesis. The coordination of the Cu^II ion is distorted square pyramidal in (I) and distorted trigonal bipyramidal in (II). The new in situ generated tridentate BDPA ligand can act as a meridional or facial ligand during the process of coordination. The crystal structures of these two compounds are stabilized by classical hydrogen bonding as well as intricate nonclassical hydrogen‐bond interactions.     

[Bis(3,5‐dimethylpyrazol‐1‐yl‐κN2)hydro(pyrazol‐1‐yl‐κN2)borato][(3,5‐dimethylpyrazol‐1‐yl‐κN2)dihydro(pyrazol‐1‐yl‐κN2)borato]nickel(II)

The title compound, [Ni(C₈H₁₂BN₄)(C₁₃H₁₈BN₆)] or Bp′Tp′Ni^II, where Bp′ is (3,5‐dimethylpyrazol‐1‐yl)dihydro(pyrazol‐1‐yl)borate and Tp′ is bis(3,5‐dimethylpyrazol‐1‐yl)hydro(pyrazol‐1‐yl)borate, contains a divalent Ni^II centre bound by the chelating N atoms of the polysubstituted pyrazolylborate ligands. It is shown to lack a strong agostic B—H...Ni interaction, implying that the sixth coordination site is unoccupied in the solid state. This square‐pyramidal complex is the only known crystal structure where the Ni^II centre is pentacoordinated while bonded exclusively to pyrazolyl units. This is of interest with respect to electrochemical and catalytic properties.     

Crystallographic report: Diiodo[tris(2‐pyridyl)amine]mercury(II), [(C5H4N)3N]HgI2

In mononuclear HgI₂[(C₅H₄N)₃N], mercury is tetrahedrally coordinated by two nitrogen atoms of a tris(2‐pyridyl)amine ligand and two iodides. The coordination moieties are connected by weak intermolecular Hg(II)···I interactions to give a one‐dimensional structure. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis,structural characterization and catalytic activities of dicopper(II) complexes derived from tridentate pyrazole‐based N2O ligands

A group of a diverse family of dinuclear copper(II) complexes derived from pyrazole‐containing tridentate N₂O ligands, 1,3‐bis(3,5‐dimethylpyrazol‐1‐yl)propan‐2‐ol (Hdmpzpo), 1,3‐bis(3‐phenyl‐5‐methyl pyrazol‐1‐yl)propan‐2‐ol (Hpmpzpo) and 1,3‐bis(3‐cumyl‐5‐methylpyrazol‐1‐yl)propan‐2‐ol (Hcmpzpo), were synthesized and characterized by elemental analysis, IR spectroscopy and three of them also by single‐crystal X‐ray diffraction. Three complexes, [Cu₂(pmpzpo)₂](NO₃)₂·2CH₃OH ( 3 ·2CH₃OH), [Cu₂(pmpzpo)₂](ClO₄)₂ ( 4 ) and [Cu₂(cmpzpo)₂](ClO₄)₂·2DMF ( 7 ·2DMF), each exhibits a dimeric structure with a inversion center being located between the two copper atoms. The metal ion is coordinated in a distorted square planar environment by two pyrazole nitrogen atoms and two bridging alkoxo oxygen atoms. Both complexes 1 ·CH₃OH·H₂O and 3 ·2CH₃OH were investigated in anaerobic conditions for the catalytic oxidation of 3,5‐di‐tert‐butylcatechol (3,5‐DTBC) to the corresponding quinone (3,5‐DTBQ), for modeling the functional properties of catechol oxidase. Copyright © 2007 John Wiley & Sons, Ltd.     

A new three‐dimensional CdII supramolecular framework constructed from the 1‐[(1H‐tetrazol‐5‐yl)methyl]‐1,4‐diazoniabicyclo[2.2.2]octane ligand

A new tetrazole–metal supramolecular compound, di‐μ‐chlorido‐bis(trichlorido{1‐[(1H‐tetrazol‐5‐yl‐κN²)methyl]‐1,4‐diazoniabicyclo[2.2.2]octane}cadmium(II)), [Cd₂(C₈H₁₆N₆)₂Cl₈], has been synthesized and structurally characterized by single‐crystal X‐ray diffraction. In the structure, each Cd^II cation is coordinated by five Cl atoms (two bridging and three terminal) and by one N atom from the 1‐[(1H‐tetrazol‐5‐yl)methyl]‐1,4‐diazoniabicyclo[2.2.2]octane ligand, adopting a slightly distorted octahedral coordination geometry. The bridging bicyclo[2.2.2]octane and chloride ligands link the Cd^II cations into one‐dimensional ribbon‐like N—H...Cl hydrogen‐bonded chains along the b axis. An extensive hydrogen‐bonding network formed by N—H...Cl and C—H...Cl hydrogen bonds, and interchain π–π stacking interactions between adjacent tetrazole rings, consolidate the crystal packing, linking the poymeric chains into a three‐dimensional supramolecular network.     

Crystallographic report: Diiodo[tris(2‐pyridyl)amine]zinc(II), [(C5H4N)3N]ZnI2

The zinc(II) atom in the molecule of [(C₅H₄N)₃N]ZnI₂ is tetrahedrally coordinated to two nitrogen atoms of the tris(2‐pyridyl)amine ligand and two iodides. The coordination moieties are connected to give a linear structure by intermolecular π–π interactions between the pyridyl rings. Copyright © 2003 John Wiley & Sons, Ltd.     

Dichloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methane]zinc(II) and di‐μ‐chloro‐bis­{chloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methane]cadmium(II)}

The Zn atom in dichloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)­methane]zinc(II), [ZnCl₂(C₁₁H₁₆N₄)], (I), is tetra­hedrally coordinated by two N atoms from one bis­(3,5‐dimethyl­pyrazol­yl)methane ligand and two terminal Cl atoms. The mol­ecule has no crystallographic symmetry. One H atom of the CH₂ group of the bis­(3,5‐dimethyl­pyrazol­yl)methane ligand inter­acts with a Cl atom of an adjacent mol­ecule to yield inter­molecular C—H⋯Cl contacts, thereby forming a one‐dimensional zigzag chain extending along the b axis. On the other hand, in di‐μ‐chloro‐bis­{chloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methane]cadmium(II)}, [Cd₂Cl₄(C₁₁H₁₆N₄)₂], (II), each of the two crystallographically equivalent Cd atoms is penta­coordinated by two N atoms from one bis­(3,5‐dimethyl­pyrazol­yl)methane ligand, and by one terminal and two bridging Cl⁻ anions. The mol­ecule has a crystallographic centre of symmetry located at the mid‐point of the Cd⋯Cd line. One H atom of the CH₂ group of the bis­(3,5‐dimethyl­pyrazolyl)­methane ligand inter­acts with a Cl atom of an adjacent mol­ecule to produce pairwise inter­molecular C—H⋯Cl contacts, thereby affording chains of mol­ecules running along the c axis.     

Synthesis and Crystal Structures of the Molybdenum(II) Complexes with the N,N‐dimethylthiocarbamoyl Containing Ligand: Crystal Structures of β [Mo(CO)2{η2‐S2P(OEt)2}(η2‐SCNMe2)(PPh3)] and [Mo(CO)2(η3‐Tp)(η2‐SCNMe2)(PPh3)]

Reactions of the thiocarbamoyl‐molybdenum complex [Mo(CO)₂(η²‐SCNMe₂)(PPh₃)₂Cl] 1 , and ammonium diethyldithiophosphate, NH₄S₂P(OEt)₂, and potassium tris(pyrazoyl‐1‐yl)borate, KTp, in dichloromethane at room temperature yielded the seven coordinated diethyldithiophosphate thiocarbamoyl‐molybdenum complexe [Mo(CO)₂{η²‐S₂P(OEt)₂}(η²‐SCNMe₂)(PPh₃)] β‐3 , and tris(pyrazoyl‐1‐yl)borate thiocabamoyl‐molybdenum complex [Mo(CO)₂(η³‐Tp)(η²‐SCNMe₂)(PPh₃)] 4 , respectively. The geometry around the metal atom of compounds β‐3 and 4 are capped octahedrons. The α‐ and β‐isomers are defined to the dithio‐ligand and one of the carbonyl ligands in the trans position in former and two carbonyl ligands in the trans position in later. The thiocabamoyl and diethyldithiophosphate or tris(pyrazoyl‐1‐yl)borate ligands coordinate to the molybdenum metal center through the carbon and sulfur and two sulfur atoms, or three nitrogen atoms, respectively. Complexes β‐3 and 4 are characterized by X‐ray diffraction analyses.     

Bis(acetonitrile‐κN)bis[hydridotris(3,5‐dimethylpyrazol‐1‐yl‐κN2)borato]di‐μ3‐sulfido‐tetra‐μ2‐sulfido‐di‐μ2‐thiocyanato‐κ2N:S;κ2S:N‐tetracopper(I)ditungsten(VI)

Reactions of (Et₄N)[Tp*WS₃] [Tp* is hydridotris(3,5‐dimethylpyrazol‐1‐yl)borate] with CuSCN in MeCN in the presence of melamine afforded the title neutral dimeric cluster [Cu₄W₂(C₁₅H₂₂BN₆)₂(NCS)₂S₆(C₂H₃N)₂] or [Tp*W(μ₂‐S)₂(μ₃‐S)Cu(μ₂‐SCN)(CuMeCN)]₂, which has two butterfly‐shaped [Tp*WS₃Cu₂] cores bridged across a centre of inversion by two (CuSCN)⁻ anions. The S atoms of the bridging thiocyanate ligands interact with the H atoms of the methyl groups of the Tp* units of a neighbouring dimer to form a C—H...S hydrogen‐bonded chain. The N atoms of the thiocyanate anions interact with the H atoms of the methyl groups of the Tp* units of neighbouring chains, affording a two‐dimensional hydrogen‐bonded network.