Copper (II) complexes of sterically hindered o-diphenol derivatives: synthesis, characterization and microbiological studies

Cu (II) complexes with the sterically hindered diphenol derivatives 3,5-di(tert-butyl)-1,2-benzenediol (I), 4,6-di(tert-butyl)-1,2,3-benzenetriol (II) and the sulfur-containing 4,6-di(tert-butyl)-3-(2-hydroxyethylsulfanyl)-1,2-benzenediol (III) and 2-[4,6-di(tert-butyl)-2,3-dihydroxyphenylsulfanyl]acetic acid (IV) have been synthesized and characterized by elemental analysis, TG/DTA, FT-IR, ESR, XPS, XPD and conductivity measurements. Compounds I–III can coordinate in their singly deprotonated forms and act as bidentate ligands. These compounds yield Cu (II) complexes of the stoichiometry Cu(L)₂, which have square planar geometry (g_| > g_⊥ > g_e). Unlike them, compound IV behaves as a terdentate ligand, and its complex Cu(L^IV)₂ has distorted octahedral geometry. According to ESR data, only the Cu(L^II)₂ complex contains a very small amount of phenoxyl radicals. Antimicrobial activities of these ligands and their respective Cu (II) complexes have been determined with respect to Gram-positive and Gram-negative bacteria, as well as on yeasts. Their phytotoxic properties against Chlorella vulgaris 157 were also examined.     

COPPER(II) COORDINATION COMPOUNDS: CLASSIFICATION AND ANALYSIS OF CRYSTALLOGRAPHIC AND STRUCTURAL DATA III. DIMERIC COMPOUNDS

Abstract

This review summarizes the data for over nine hundred dimeric Cu(II) coordination compounds. There are several types of the bridges, from which doubly bridges by far prevail. The most common ligands are O? and N? donors. From the stereochemical point of view, a square-pyramidal arrangement with different degrees of distortion about Cu(II), is the most common. Several relationships were found between the Cu-Cu distances and the Cu-L-Cu bridge angle and the type of bridging, between the intra-ligand L-Cu-L ring angles and coordination numbers.     

INFRARED ASSIGNMENT OF BIS(GLYCOLATO)-BIS(PYRIDINE) METAL(II) COMPOUNDS AND CRYSTAL STRUCTURE OF TRANS-BIS(GLYCOLATO)-CIS-BIS(PYRIDINE)NICKEL(II) DIHYDRATE

Abstract

Infrared spectra of the coordination compounds [MG₂(py)₂], M(II)=Co, Ni, Cu and Zn; G=glycolato, py=pyridine, have been fully assigned by means of py and py-d ₅ and glycolato α—OH and α—OD (G-d) labelling as well as metal ion substitution in the 4000–70cm^?1 region. The crystal structure of the Ni(II) compound is presented and the spectra of the compounds are discussed on the basis of their structure and their bonding to the glycolato and pyridine ligands. Vibrational frequencies obtained for the Ni(II) compound are compared to those obtained by calculations carried out using the Gaussian 94 program package.     

Synthesis,characterization, and crystal structures of cobalt(II), copper(II), and zinc(II) complexes of a bidentate iminophenol

A bidentate iminophenol (HL = 2-((4-methoxyphenylimino)methyl)-4,6-di-tert-butylphenol derived from condensation of 4-methoxyaniline and 3,5-di-tert-butyl-2-hydroxybenzaldehyde) was mixed with divalent metal salts to form the corresponding mononuclear metal complexes [M^II(L)₂] (M = Co (1), Cu (2), and Zn (3)). The complexes are characterized by different spectroscopic and analytical tools. X-ray crystal structures of the complexes revealed homoleptic mononuclear complexes with MN₂O₂ coordination. The cobalt(II) (1) and zinc(II) (3) complexes display a pseudo-tetrahedral coordination geometry, whereas the copper(II) complex (2) exhibits a distorted square-planar coordination. The zinc(II) complex (3) emits at 460 nm with a twofold enhancement of emission with respect to the free iminophenol.     

Crystal Structure of Bis -(2,2′-bipyridine-N,N′)-(dicyanamide-N)-copper(II) Tricyanomethanide. Electronic and Structural Parameters Describing the Shape of Coordination Polyhedra in Five-Coordinated Copper(II) Compounds

 The structure of the new compound [Cu(bpy)₂N(CN)₂]C(CN)₃ (6) is compared with thestructures of six copper(II) coordination compounds with phenanthroline or bipyridine ligands and N-donor pseudohalide anions: [Cu(phen)₂NCS]C(CN)₃ (1), [Cu(bpy)₂NCS]C(CN)₃ (2), [Cu(phen)₂NCS]ONC(CN)₂ (3), [Cu(phen)₂N(CN)₂]C(CN)₃ (4), [Cu(bpy)₂C(CN)₃]C(CN)₃ (5), and [Cu(bpy)₂NCO]C(CN)₃ (7). The Cu(II) atoms in all above compounds are five-coordinated with an N-donor atom of the pseudohalide anion located in the equatorial plane of a deformed trigonal bipyramid. The shape of the coordination polyhedra and the degree of trigonal bipyramidal distortion towards a tetragonal pyramid are discussed and described using one electronic and several structural criteria which are discussed and compared.     

Metal(II) complexes and metal(II) salts ofN-carbamoylpyrazole: N,O and N,N coordination

Summary Several new coordination compounds are reported withN-carbamoylpyrazole (Hcpz) as the ligand;viz. M(cpz)₂ where M = Cu^II and Ni^II; M(Hcpz)Cl₂ where M = Mn^II, Co^II, Cu^II, Zn^II and Cd^II; M(Hcpz)₂Cl₂ Where M = Fe^II, Co^II and Ni^II: M(Hcpz)₃(BF₄)₂ where M = Fe^II, Co^II, Ni^II, Zn^II and Cd^II; and Cu(Hcpz)₂(BF₄)₂. In the salts, Hcpz is coordinated through the nitrogen atoms of the pyrazole ring and the nitrogen atom of the carbamoyl group. In the Hcpz complexes, coordination takes place through the nitrogen atom of the pyrazole ring and the oxygen atom of the carbamoyl group.     

STRUCTURES AND PROPERTIES OF COPPER(II) COMPLEXES WITH IMINODIACETATO AND IMIDAZOLE OR RELATED LIGANDS. I. CRYSTAL STRUCTURE OF AQUA(IMIDAZOLE) (IMINODIACETATO)COPPER(II) MONOHYDRATE AND (IMIDAZOLE)(N-CARBOXYMETHYL-D,L-THREONINATO)COPPER(II)

Abstract

The crystal structures of two mixed-ligand copper(II) complexes having iminodiacetate(2-) (IDA) or N-carboxymethyl-D,L-threoninato(2-) ion (CMT) as terdentate ligands and imidazole (ImH) as an N-heterocyclic ligand are reported. Both compounds crystallize in the orthorhombic system, space group Pbca with Z = 8. Aqua(imidazole)(iminodiacetato)copper(II) monohydrate (I,R = 0.065, R _w = 0.075) consists of H₂O molecules and [Cu(IDA)(ImH)(H₂O)] complex units in a hydrogen bonding network. The structure of imidazole(N-carboxymethyl)-D,L-threoninatocopper(II) (IV, R = 0.066, Rω 0.078) is built up of hydrogen bonded polynuclear chains. In both compounds the Cu(II) ion exhibits a flattened and distorted square-based pyramidal coordination, with a terdentate aminoacidate ion, IDA or CMT, and one ImH ligand at the base and H₂O (in I) or the oxygen atom of the OH side chain from one adjacent CMT ion (in IV) as the fifth apical ligand. The nearly coplanar conformation of the two five-membered chelate rings in I and IV is discussed in connection with the known structure of corresponding aquacomplexes (with H₂O instead of ImH) and the ability of terdentate aminoacids to give ternary Cu(II) complexes having two N-heterocyclic donors (2 ImH or one 2,2′-bipy) per Cu(II) atom.     

An investigation of the thermal behavior of heterobimetallic species containing copper(II) and tetracyanopalladate(II)

Synthesis, characterization and thermal behavior of four compounds that have the general formula [Cu{Pd(CN)₄}(L)_x]_n, in which en=1,2-diaminoethane and pn=1,3-diaminopropane (L=en, x=1 (I); L=pn, x=1 (II); L=en, x=2 (III); L=pn, x=2 (IV)) were described in this work. The complexes were studied by elemental analysis, infrared spectroscopy (IR), differential thermal analysis (DTA) and thermogravimetry (TG) and the residues of the thermal decomposition were characterized by X-ray powder diffraction and found as a mixture of CuO and PdO. The stoichiometry of the compounds was established via thermogravimetric and elemental analyses and their structures were proposed as coordination polymers based on their infrared spectra. The following thermal stability sequence was found: IV<I=II<III.     

Co(II), Ni(II), and Cu(II) Complexation with Isatin Aminoguanisone and Nitroaminoguanisone

New complexes of bivalent Co, Ni, and Cu with isatin aminoguanisone (HL) and nitroaminoguanisone (HL¹) of the composition ([Co(HL)₂]Cl₂ (I), [Ni(HL)₂]Cl₂ (II), [Cu(L)Cl] (III), [Co(L¹)₂] (IV), [Ni(L¹)₂] (V), and [Cu(L¹)₂] (VI) are synthesized. Their molecular conductivities and effective magnetic moments are measured and thermal stabilities are studied. The type of the ligand coordination in I–VI is proposed on the basis of IR data. The summary of physicochemical data for I–VI and the energy calculations for their molecules by the molecular mechanics method made it possible to establish stoichiometry of the coordination polyhedra of the complexes.     

Synthesis,structure, cytotoxic activities,and DNA-binding of 1-D copper(II) and zinc(II) coordination polymers

Two 1-D coordination polymers have been synthesized and identified as [Zn(ox)(en)] _n (H₂O)_{2 n} (1) and [Cu₂(dmeo)(N₃)₂] _n (2), where en represents diaminoethane, ox and dmeo stand for dianions of oxalic acid and N,N′-bis[2-(dimethylamino)ethyl]oxamide, respectively. Polymer 1 was characterized by elemental analysis, molar conductance measurement, IR and electronic spectra, and single-crystal X-ray diffraction. Polymer 1 consists of 1-D chains bridged by oxalate. The Zn^II can be described as a distorted octahedral environment and the Zn^II···Zn^II separation through the μ-oxalato-bridge is 5.5420(9)?Å. Hydrogen bonds assemble the coordination polymers to a 3-D supermolecular structure. The crystal structure of 2 has been reported previously. However, the bioactivities were not studied. The DNA-binding properties and cytotoxic activities of the two coordination polymers are investigated. The results suggest that the two polymers interact with HS-DNA in groove binding with binding affinity following the order of 1?>?2, which is consistent with their anticancer activities.     

Thermal and spectral properties of Cu(II)-5-halogenosalicylates with or without nicotinamide

Summary This paper deals with the preparation and investigation of thermal and spectral properties of the complexes Cu(5-ClSal)₂·2H₂O (I), Cu(5-BrSal)₂·2H₂O (II), Cu(5-ClSal)₂(nia)(H₂O) (III), Cu(5-BrSal)₂(nia)(H₂O) (IV), and Cu(5-ISal)₂(nia)(H₂O) (V) (where Sal=salicylate, and nia=nicotinamide). TG, DTG, DTA, EPR, IR and electronic spectra have been used to study thermal and spectral properties of the complexes. The chemical composition of the complexes, the solid intermediates and the resultant products of thermolysis have been identified by means of elemental analysis and complexometric titration. Schemes of the decomposition of the complexes are suggested. Heating of the compounds first resulted in the release of water molecules. The thermal stability of these complexes can be ordered in the sequence: I <II <IV=V< III. The final product of the thermal decomposition was CuO in all cases. IR data suggested a bidentate coordination of carboxylates to Cu(II) in complexes I-II and bridging ones for complexes III-V.     

Preparation and characterization of Cu(II)-N-salicylideneanthranilic acids,their reduction products and hydrolysis of the Schiff base

Copper (II) complexes ofN-salicylideneanthranilic acid (I) and its derivatives (II, III) as well as their NaBH₄ reduction products, namelyN-(2-hydroxybenzyl) anthranilic acids (IV–VI) have been prepared and their structures have been determined analytically. Tetracoordinated planar structures of the Cu(II) complexes of the Schiff bases and distorted tetrahedral structures of the Cu(II) complexes of compoundsV–VI have been elucidated by ESR and other spectral methods. During the preparation of the complex the hydrolysis of the Schiff base often takes place in the presence of water giving anthranilates and salicylaldehydates of metals to some extent along with the complexes of the Schiff base. The kinetic data for the hydrolysis ofN-salicylideneanthranilic acid (I) in methanol-water solution also are reported.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August, 1995.     

Metal Chelates of N‐(2‐pyridylmethyl)iminodiacetate(2‐) Ion (pmda). Part II. Ternary pmda Chelates with M = Co,Cu or Zn and Creatinine as Auxiliary Ligand

The compounds [Cu(pmda)(crea)]·H₂O ( 1 ), [Zn(pmda)(crea)]·H₂O ( 2 ) and [Co(pmda)(crea)(H₂O)]·H₂O ( 3 ) were prepared and characterized by thermal, spectral and X‐ray diffraction methods. In compounds 1 and 2 the M^II coordination is of type 4+1 and approaches to a trigonal bipyramid (71.85 and 86.18 %, respectively) with rather linear N(pmda)‐M^II‐N(crea) trans‐apical angles, but with different longest coordination bond (Cu‐O(pmda) or Zn‐N(apliphatic, pmda), respectively). Both compounds are isotypic and one intra‐molecular interligand N‐H···O interaction reinforces the molecular recogniton crea‐M^II(pmda) chelate. In contrast, the compound 3 exhibits an octahedral coordination, imposed by the 3d⁷ electronic configuration of the cobalt(II) atom, and the crea‐chelate recognition involves the Co‐N(crea) coordination bond and one intramolecular ‘bifurcated’ H‐bonding interaction between one N‐H(crea) bond and one O(pmda) plus the O(aqua) atoms as ‘acceptors’.     

Ion‐Directed Coordinative Polymerization of Copper(II) Pyridyl‐Alcohol Complexes Through Thiane Functionalities

A mononuclear complex [Cu(HL · S)₂(NO₃)₂] ( 1 ) and a one‐ dimensional coordination polymer [Cu(HL · S)Cl₂]_n ( 2 ) [HL · S = 4‐(pyridin‐2‐ylmethyl)tetrahydro‐2H‐thiopyran‐4‐ol] showcase the structure‐directing role of the counterions in their formation reaction: monodentate ligation of NO₃^– and Cl^– induces an octahedral (with two HL · S per Cu in 1 ) or trigonal‐bipyramidal (with one HL · S per Cu in 2 ) Cu^II coordination environment. In contrast to 1 exhibiting no coordinative metal–sulfur bonds in the crystal lattice (space group P2₁/c), 2 (P2₁/c) features intermolecular Cu–S contacts of 2.3188(7) Å. The coordination compounds are thermally stable up to ca. 160 °C. Whereas 1 demonstrates the spin‐like behavior of an isolated central Cu^II ion, compound 2 exhibits weak antiferromagnetic intra‐chain coupling with J ≈ –2.1 cm^–1 between neighboring Cu^II ions.     

COPPER(II) COORDINATION COMPOUNDS: CLASSIFICATION AND ANALYSIS OF CRYSTALLOGRAPHIC AND STRUCTURAL DATA. V. POLYMERIC COMPOUNDS

Abstract

This review classifies almost 600 polymeric Cu(II) compounds. The various geometries are found in increasing number in the order: four-(mostly square-planar) ? five- (mostly square-pyramidal) ? six-coordinate (mostly tetragonal-bipyramidal). The most common ligands are oxygen and nitrogen atoms. The ligands range from mono- to undecadentate. In most examples, apical positions are occupied by oxygen-donor ligands. In general, the mean Cu-L(equatorial) bond length is shorter than the respective Cu-L(apical) bond length. The shortest Cu-Cu distance in the series of four-coordinate derivatives is 2.95 Å, five-coordinate 2.652(2) Å and six-coodinate 2.977(2) Å. Several relationships between the various structural parameters were found and are discussed.     

THE SYNTHESIS AND CHARACTERIZATION OF A NOVEL vic-DIOXIME AND ITS MONO AND TRINUCLEAR COMPLEXES CARRYING A TRIOXADITHIA MACROCYCLE

Abstract

A new vicinal dioxime, l,15-bis(hydroxyimino)-2,14-dithia-5,8,11-trioxacyclopentadecane (H₂L) was synthesized by the reaction of (E,E)-dichloroglyoxime (1) with 1,11-dithio-3.6.9-trioxaundecane (2). Mononuclear copper(II) complexes with a metal/ligand ratio of 1/2 were prepared. The two ligands coordinate to copper(II) through the deprotonated oximate oxygens which then afford the trinuclear structure bridged by the oximate groups with 1,10-phenan-throline or 2,2′-dipyridyl as the end-cap ligand.     

(2‐Aminopyrimidine‐κN1)aqua(pyridine‐2,6‐dicarboxylato‐κ3O2,N,O6)copper(II): X‐ray and DFT calculated structure

In the title compound, [Cu(C₇H₃N₂O₄)(C₄H₅N₂)(H₂O)], (I), pyridine‐2,6‐dicarboxylate (pydc²⁻), 2‐aminopyrimidine and aqua ligands coordinate the Cu^II centre through two N atoms, two carboxylate O atoms and one water O atom, respectively, to give a nominally distorted square‐pyramidal coordination geometry, a common arrangement for copper complexes containing the pydc²⁻ ligand. Because of the presence of Cu...X_bridged contacts (X = N or O) between adjacent molecules in the crystal structures of (I) and three analogous previously reported compounds, and the corresponding uncertainty about the effective coordination number of the Cu^II centre, density functional theory (DFT) calculations were used to elucidate the degree of covalency in these contacts. The calculated Wiberg and Mayer bond‐order indices reveal that the Cu...O contact can be considered as a coordination bond, whereas the amine group forming a Cu...N contact is not an effective participant in the coordination environment.     

Syntheses, magnetic and spectral studies on polystyrene supported coordination compounds of bidentate and tetradentate Schiff bases

The reaction of aminomethylated polystyrene (PSCH₂-NH₂) and 2-hydroxyacetanilide in DMF results in the formation of polystyrene-anchored monobasic bidentate Schiff base, PSCH₂-LH (I). On the other hand, the reaction of chloromethylated polystyrene (PSCH₂-Cl), 3-formylsalicylic acid, ethylenediamine and acetylacetone in DMF in presence of ethyl acetate (EA) and triethylamine (TEA) produces another polystyrene-anchored dibasic tetradentate Schiff base, PSCH₂-L′H₂ (II). BothI andII react with a number of di-, tri-and hexavalent metal ions like Co, Ni, Cu, Zn and Cd to form polystyreneanchored coordination compounds, and these have been characterized and discussed.     

通过铜(II)、铁(III)和铁(II)与2,2'-联咪唑协同作用构筑的超分子及其结构的研究

在水和乙醇溶剂中, 通过Cu(II), Fe(III)和Fe(II)与2,2-联咪唑协同作用, 构筑了四种新的超分子配合物[Cu(H₂biim)(gly)(H₂O)]Cl•H₂O (1), [Cu(H₂biim)(C₃H₂O₄)(H₂O)]•1.5H₂O (2), [Fe₂(μ-O)(H₂biim)₄(H₂O)₂](NO₃)₄•C₂H₅OH (3)和[Fe(H₂biim)₃]SO₄ (4) (H₂biim＝2,2-联咪唑; gly^－＝甘氨酸根; C₃H₂O＝丙二酸根). 并通过元素分析, 红外光谱和X射线单晶衍射对其组成、结构和谱学性质进行研究. H₂biim配体, 丙二酸根和甘氨酸根三种配体都采用了双齿螯合方式与金属离子配位. 配合物1～4中, 通过H₂biim配体的N—H键与阴离子、水分子和溶剂分子形成多种氢键, 如R(7), R(9)和R(4)等, 以及H₂biim配体之间的π-π堆积, 阳离子不对称单元构筑了多维结构的超分子配合物.     

Synthesis,spectral and thermal properties of macrocyclic zinc(II) complexes

The new zinc ternary complexes [Zn(cyclen)NO₃]ClO4 (I), [Zn₂(cyclen)₂(m-nic)](ClO₄)₃ (II), [Zn₂(cyclen)₂(m-pic)](ClO₄)₃ (III) (cyclen=1,4,7,10-tetraazacyclododecane; nic=nicotinic acid; pic=picolinic acid) were synthesized and their spectral and thermal properties were investigated. The compounds were characterized by elemental analysis, IR spectroscopy and TG/DTG, DTA methods. Moreover, the way of coordination of pyridinecarboxylate anions was proposed on the basis of the spectral data and consequently proved with results of X-ray structure analysis. This revised version was published online in August 2006 with corrections to the Cover Date.