DNA binding, nuclease activity, DNA photocleavage and cytotoxic properties of Cu(II) complexes of N-substituted sulfonamides.

Abstract Ternary copper(II) complexes [Cu(NST)2(phen)] (1) and [Cu(NST)2(NH3)2]·H2O (2) [HNST = N-(4,5-dimethylthiazol-2-yl)naphthalene-1-sulfonamide] were prepared and characterized by physico-chemical techniques. Both 1 and 2 were structurally characterized by X-ray crystallography. The crystal structures show the presence of a distorted square planar CuN4 geometry in which the deprotonated sulfonamide, acting as monodentate ligand, binds to the metal ion through the thiazole N atom. Both complexes present intermolecular π–π stacking interactions between phenanthroline rings (compound 1) and between naphthalene rings (compound 2). The interaction of the complexes with CT DNA was studied b…

Copper(II) complexes with sulfonamides derived from 2-picolylamine and their use as chemical nucleases

Reaction between 2-picolylamine (2-aminomethylpyridine) with 2-mesitylenesulfonyl and 4- tert -butylbenzene sulfonyl chlorides leads to the formation of 2,4,6-trimethyl- N -[pyridin-2-ilmethyl]benzenesulfonamide (Hpmesa) and 4-ter-butyl- N -[pyridin-2-ilmethyl]benzenesulfonamide (Hptbsa). These compounds react with Cu(II) salts to yield coordination compounds with CuL 2 stoichiometry. The immediate environment of the metal ion is a highly distorted tetrahedron, the sulfonamide ligands acting in a bidentate fashion. Compound Hpmesa crystallizes in monoclinic space group P 2 1 /c (number 14), with Z  = 4; complex [Cu(pmesa) 2 ] crystallizes in monoclinic space group P 1 ¯ (number 2), with Z  …

Functional superoxide dismutase mimics. Structural characterization and magnetic exchange interactions of copper(II)-N-substituted sulfonamide dimer complexes.

Dinuclear copper(II) complexes with N-substituted sulfonamide ligands as superoxide dismutase (SOD) mimics have been investigated. The new N-(thiazol-2-yl)toluenesulfonamide (Htz-tol) and N-(thiazol-2-yl)naphthalenesulfonamide (Htz-naf) ligands have been prepared and structurally characterized. The complexes derived from these ligands, [Cu(2)(tz-tol)(4)] (1) and [Cu(2)(tz-naf)(4)] (2), have been synthesized, and their crystal structure, magnetic properties, and EPR spectra were studied in detail. In both compounds the metal centers are bridged by four nonlinear triatomic NCN groups. The coordination geometry of the coppers in the dinuclear entity of 1 and 2 is distorted square planar with t…

Crystal structure of [Cu(N-quinolin-8-yl-p-toluenesulfonamidate)2]: study of its interaction with DNA and hydrogen peroxide

A new copper complex with N-quinolin-8-yl-p-toulenesulfonamide has been prepared and characterised. The compound crystallises in the triclinic system, space group P1, with a=13.457(3), b=15.067(5), c=18.589(3) A; α=112.05(2), β=93.92(2), γ=108.30(2)° and Z=4. The geometry of the Cu(II) ion is distorted square planar. The N-quinolin-8-yl-p-toulenesulfonamidate anion behaves as a bidentate ligand through the N s u l f o n a m i d a t e and N q u i n o l i n e atoms. The complex does not cleave DNA in the presence of hydrogen peroxide.

Synthesis, Characterization, and Properties of Some Copper( II ) Complexes of 2‐Pyridineformamide Thiosemicarbazone (HAm4DH)

Reactions between different copper(II) salts and 2-pyridineformamide thiosemicarbazone (HAm4DH) in neutral ethanolic media led to the formation of complexes with the formulae [Cu(HAm4DH)X2] (X = Cl or Br) (1, 2) and [Cu(HAm4DH)2]X2 (X = NO3 or ClO4) (3, 4). The same reactions carried out in the presence of triethylamine gave rise to new complexes with the general formulae [Cu(Am4DH)X] (X = Cl, Br, AcO, or NO3) (5–8), [Cu(H2O)(Am4DH)](ClO4) (9), and [Cu(Am4DH)2] (10), many of which were isolated with different molecules of crystallization and contain a deprotonated thiosemicarbazone (Am4DH). These complexes were characterized by elemental analysis, and different spectroscopic and magnetic te…

Synthesis, Crystal Structures and Properties of [Cu(L1)2(py)2(H2O)](H2O) [HL1 = N-(5-ethyl-[1,3,4]–thiadiazole-2-yl)-toluenesulfonamidate] and [Cu(L2)2(py)2(H2O)] [HL2 = N-(5-ethyl-[1,3,4]–thiadiazole-2-yl)-benzenesulfonamidate]

A series of new N-sulfonamidate ligands and their cooper(II) complexes, [Cu(N-(5-ethyl-[1,3,4]-thiadiazole-2-yl)-toluenesulfonamidate)2(py)2(H2O)](H2O) (1) and [Cu(N-(5-ethyl-[1,3,4]-thiadiazole-2-yl)-benzenesulfonamidate)2(py)2(H2O)] (2) have been synthesized and characterized. The X-ray crystal structures of the complexes 1 and 2 have been determined. In the both two complexes, the Cu2+ ion is five-coordinated, forming a CuN4O chromophore. The ligands act as monodentate, coordinating the metal ion through a single Nthiadiazole atom. The molecules from the reaction medium (pyridine and water) also participate to the coordination of Cu2+ ion as monodentate ligands. Both two complexes have a…

Synthesis, crystal structure and properties of two acetazolamide (5-acetamido-1,3,4-thiadiazole-2-sulfonamide) complexes: bis(5-acetamidato- 1,3,4-thiadiazole-2-sulfonamide-O)bis( 1,2-ethanediamine)copper(II) and bis(5-acetamidato-1,3,4-thiadiazole-2-sulfonamide-N)bis(1,3- propanediamine)copper(II); an unusually weak ambidentate anionic ligand

Abstract The diverse coordination chemistry exhibited by acetazolamide (H2acm), a potent inhibitor of the carbonic anhydrase metalloenzyme, is highlighted in two new copper(II) complexes of this ligand: [Cu(Hacm)2(en)2] (I) and [Cu(Hacm)2(tn)2] (II). The synthesis, crystal structure and spectroscopic properties of both compounds are reported in this paper. The structures of both compounds consist of discrete units of [Cu(Hacm)2(en)2] (I) and [Cu(Hacm)2(tn)2] (II), respectively, interacting through van der Waals contacts and hydrogen bonds only. Hacm, however, binds differently in each compound. In both cases, the Cu(II) ions, lying on the symmetry centers, show an elongated octahedral geome…

Metal complexes of sulfanilamide derivatives. Spectroscopic characterization of the dichloro disulfathiazole methanol copper(II) complex

The synthesis and spectral characterization of the [Cu(Hstz)2(MeOH)Cl2] complex are described. Both polycrystalline powder EPR and single crystal EPR spectra recorded at room temperature show rhombic distortion with values of g1=2.25, g2=2.09 and g3=2.03 in agreement with a copper polyhedron, intermediate between trigonal bipyramid and square pyramidal.

Copper(II) Polyamine Complexes withN-Benzothiazole Sulfonamides as Counterions — Synthesis, Crystal Structures, and Properties of [Cu(dien)2](L1)2[HL1 =N-2-(benzothiazole)naphtalenesulfonamide, dien = diethylentriamine] and [Cu(en)2(H2O)2](L2)2[HL2 =N-2-(6-chlorobenzothiazole)toluenesulfonamide, en = ethylenediamine] — Superoxide Dismutase-like Activity

Copper(II) complexes of new N-benzothiazole sulfonamides (HL1= N-2-(benzothiazole)naphtalensulfonamide and HL2 = N-2-(6-chlorobenzothiazole)toluenesulfonamide) with ethylenediamine (en) and diethylenetriamine (dien) have been synthesized and characterised. The crystal structures of [Cu(dien)2](L1)2 (1) and [Cu(en)2(H2O)2](L2)2 (2) compounds have been determined. The metal centre adopts a “4+2” distorted octahedral environment in both complexes. Unusually, the sulfonamidate anions act as counterions. Spectroscopic properties are in good agreement with the crystal structures. The superoxide dismutase (SOD)-like activity of complex 2 has been tested. Kupfer(II)-Polyamin-Komplexe mit N-Benzothi…

Structural characterisation and nuclease activity of mixed copper(II) complexes with sulfonamides and bipyridil

Mixed copper complexes have been synthetised through reaction of Cu(II) salts with bipyridil and N-quinolin-8-yl-p-toluenesulfonamide (Hqtsa), N-quinolin-8-yl-benzenesulfonamide (Hqbsa) or N-quinolin-8-yl-naftalenesulfonamide (Hqnsa). Single crystal X-ray diffraction structure determination shows that copper cations are five-coordinated, one complex have distorted bipyramidal trigonal geometry and the other have a distorted square-pyramid. The FT IR and EPR spectra are also reported. Electrophoresis results show that the synthetised complexes in the presence of ascorbate and hydrogen peroxide are chemical nucleases.

DNA cleavage reaction induced by dimeric copper(II) complexes of N-substituted thiazole sulfonamides

A new dinuclear copper(II) complex has been synthesised and structurally characterised: [Cu2(tz-ben)4] (Htz-ben = N-thiazol-2-yl-benzenesulfonamide). Its crystal structure, magnetic properties and electronic paramagnetic resonance (EPR) spectra were studied in detail. In the compound the metal centres are bridged by four non-linear triatomic NCN groups. The coordination geometry of the copper ions in the dinuclear entity is distorted square pyramidal (4+1). Two thiazole N and two sulfonamido N atoms occupy the equatorial positions and one sulfonamido O atom is in the axial position. Magnetic susceptibility data show a strong antiferromagnetic coupling, -2J = 114.1 cm(-1). The EPR spectra of…

Tin(II) Derivatives of 2,3-Dihydroxynaphthalene

Abstract The reaction of aqueous solutions of tin(II) chloride and 2,3-dihydroxynaphthalene (H2A) gives a white precipitate of SnA. This compound has been characterized by chemical analysis, IR spectra and thermogravimetric analysis. A spectrophotometric study of tin(II) and H2A in DMF shows the formation of two species with stoichiometric ratios Sn:H2A 1:1 and 1:2.

New Cu(II) and Zn(II) complexes of benzolamide with diethylenetriamine: synthesis, spectroscopy and X-ray structures

Abstract New benzolamide (H2bz, 5-phenylsulfonamide-1,3,4-thiadiazole-2-sulfonamide) zinc(II) and copper(II) complexes with diethylenetriamine were synthesized and characterized. The crystal structures of the [M(Hbz)2(dien)] (M=Cu(II), Zn(II); dien=diethylenetriamine) complexes were determined. The metal centre adopts a near regular square pyramidal geometry. The benzolamidate anion acts as a monodentate ligand through the thiadiazole N atom contiguous to the deprotonated sulfonamido group. Spectroscopic properties are in good agreement with the crystal structures. The EPR and electronic spectroscopic studies showed that the copper(II) species doped into the zinc(II) complex adopts a near s…

Metal complexes of the carbonic anhydrase inhibitor methazolamide (Hmacm). Crystal structure of the Zn(macm)2 (NH3)2. Anticonvulsant properties of the Cu(macm)2 (NH3)3(H2O)

Complexes of Co(II), Cu(II), and Zn(II) with deprotonated methazolamide and ammonia are synthesized and characterized. The complex Zn(macm)2(NH3)2 crystallizes in the monoclinic C2/c space group with a = 13.468(1), b = 6.759(1), c = 23.014(2) A, beta = 90.27(1), and Z = 4. The structure was refined to R = 0.049 (Rw = 0.053). The Zn(II) ion is coordinated to two deprotonated sulfonamido nitrogen atoms of the macm- ligand and two nitrogen atoms of the ammonia ligands in a distorted tetrahedron. The Zn(macm)2(NH3)2 complex is shown to be a simple model for the methazolamide inhibition of CA. EHMO calculations applied to fractional coordinates of the Zn(macm)2(NH3)2 complex indicate that the at…

Oxidative DNA cleavage by copper ternary complexes of 1,10-phenanthroline and ethylenediamine-sulfonamide derivatives

Abstract Ternary copper(II) complexes (1–3) of 1,10-phenanthroline and ethylenediamine-R-sulfonamide derivatives (R = benzene, toluene and naphthalene rings) have been synthesized and characterized with the aid of X-ray diffraction and spectroscopic and electrochemical techniques. The crystal structures of the complexes show that the coordination polyhedron around copper(II) is distorted square planar. Both 1,10-phenanthroline and ethylenediamine-R-sulfonamide act as bidentate ligands. The three structures are stabilized by π–π stacking interactions. The interaction of the complexes with calf thymus DNA has been investigated by thermal denaturation studies which indicated that DNA was stabi…

Structural and functional models for the dinuclear copper active site in catechol oxidases

Two new mu-methoxo-bridged dinuclear copper(II) complexes with a N-substituted sulfonamide, [Cu(mu-OMe)(L)(NH(3))](2) (1) and [Cu(mu-OMe)(L)(DMSO)](2) (2) [HL, N-2-(4-methylbenzothiazole)benzenesulfonamide], have been prepared and characterized by single-crystal X-ray difraction analyses. Compound 1 crystallizes in the monoclinic space group C(2)/c with a=22.0678(18), b=7.9134(7), c=21.1186(18)A, beta=113.788(4) degrees and Z=8. Compound 2 crystallizes in the monoclinic space group C(2)/c with a=18.0900(10), b=9.5720(10), c=24.2620(10) A, beta=98.7120(10) degrees and Z=8. In both complexes the copper atoms have square-planar environments bridged by two oxygen atoms from methoxide groups. Ma…

Synthesis and characterization of sulfonamides containing 8-aminoquinoline and their Ni(II) complexes. Crystalline structures of the Ni complexes

Reaction between 8-aminoquinoline and benzenesulfonyl, toluene-4-sulfonyl and naphthalene-2-sulfonyl chlorides in a basic medium leads to the formation of the corresponding sulfonamides. Reaction of these sulfonamides with Ni(II) salts leads to the formation of the corresponding complexes, with a NiL 2 stoichiometry. Determination of the crystalline structure by X-ray diffraction shows an octahedral environment for the Ni(II) ions, sulfonamides acting as bidentate ligands and two solvent molecules completing the octahedral coordination. The spectroscopic and magnetic properties of these compounds are also discussed.

Mixed-ligand copper(ii)–sulfonamide complexes: effect of the sulfonamide derivative on DNA binding, DNA cleavage, genotoxicity and anticancer activity

Four ternary complexes, [Cu(L1)2(bipy)] (1) [HL1 = N-(6-chlorobenzo[d]thiazol-2-yl)-4-methylbenzenesulfonamide], [Cu(L2)2(bipy)] (2) [HL2 = N-(benzo[d]thiazol-2-yl)-4-methylbenzenesulfonamide], [Cu(L3)2(bipy)]·1/2H2O (3) [HL3 = N-(5,6-dimethylbenzo[d]thiazol-2-yl)-4-methylbenzenesulfonamide] and [Cu(L4)2(bipy)] (4) [HL4 = N-(5,6-dimethylbenzo[d]thiazol-2-yl)benzenesulfonamide], were prepared and then characterized by X-ray crystallography, spectroscopy and magnetic measurements. Whereas the molecular structure of 1 and 2 consists of a discrete monomeric copper(II) species with a distorted square planar geometry, that of 3 and 4 consists of two independent molecules. In 3, both molecules pre…

Synthesis, crystallographic and spectroscopic characterization and magnetic properties of dimer and monomer ternary copper(II) complexes with sulfonamide derivatives and 1,10-phenanthroline. Nuclease activity by the oxidative mechanism

Abstract Three dinuclear and one mononuclear copper(II)-1,10-phenanthroline ternary complexes, [Cu(L1)(phen)(OH)]2 (1), [Cu(L2)(phen)(OH)]2·3H2O (2), [Cu(L3)(phen)(OH)]2 (3) and [Cu(L4)2(phen)(H2O)] (4), with thiadiazole sulfonamide derivative ligands: HL1 (N-(5-ethyl-1,3,4-thiadiazol-2-yl)naphthalene-1-sulfonamide), HL2 (N-(5-ethylthio)-1,3,4-thiadiazol-2-yl)-4-methylbenzenesulfonamide), HL3 (N-(5-ethyl-1,3,4-thiadiazol-2-yl)benzenesulfonamide) and HL4 (N-(5-ethyl-1,3,4-thiadiazol-2-yl)-4-methylbenzenesulfonamide) have been synthesized and characterized. In the four complexes each copper atom is five-coordinated. The structure of complexes 1, 2 and 3 consists of a dimeric unit with a C2 sy…

Crystal structures and spectroscopic properties of copper(II)–bis(2-pyridylcarbonyl)amide–chlorobenzoate complexes

The reaction of 2,4,6-tris(pyridyl)-1,3,5-triazine (ptz) and copper(II) salts in DMF–water (4:1) resulted in the hydrolysis of ptz, giving rise to the bis(2-pyridylcarbonyl)amide anion ( ptO 2 - ) and affording the complexes [Cu(ptO 2 )(2-Clbenz)(H 2 O)] ( 1 ), [Cu(ptO 2 )(3-Clbenz)] ( 2 ), and [Cu(ptO 2 )(4-Clbenz)(DMF)] ( 3 ). This report includes the chemical and spectroscopic characterization of all these compounds along with the crystal structures of the Cu(II) complexes thus formed. The coordination spheres of Cu(II) in 1 and 3 are best described as distorted square based pyramidal, while for 2 the coordination sphere is distorted square planar.

DNA interaction of new copper(II) complexes with sulfonamides as ligands

New copper(II) complexes with sulfonamide ligands have been prepared and characterized. Sulfonamide ligands were prepared through a reaction between 8-aminoquinoline and either 2-mesitylene (Hqmesa), 4-tert-butylbenzene (Hqtbsa), or alpha-toluene (Halphaqtsa) sulfonyl chlorides. The structural analysis carried out for complex [Cu(alphaqtsa)(2)] indicated that the local environment of the Cu(II) cation is between a square planar and a tetrahedral geometry, with stacking of the benzene rings of the sulfonyl ligands between neighbor molecules. Powder EPR spectra at room temperature gave rhombic spectra for the [Cu(alphaqtsa)(2)] and [Cu(qmesa)(2)] complexes and an axial spectrum for the [Cu(qt…

Efficient DNA Cleavage Induced by Copper(II) Complexes of Hydrolysis Derivatives of 2,4,6‐Tri(2‐pyridyl)‐1,3,5‐triazine in the Presence of Reducing Agents

The reaction of 2,4,6-tri(pyridyl)-1,3,5-triazine (ptz) and copper(II) salts in dmf/water (1:1) results in the hydrolysis of ptz and formation of the anions bis(2-pyridylcarbonyl)amide (ptO2–) and bis(2-pyridylamine)amide (ptN2–), which are found in the complexes [Cu(ptN2)(OAc)]·3H2O (1), [Cu(ptO2)(OAc)(H2O)]·H2O (2), [Cu(ptN2)(for)]·3H2O (3) (for = formate), [Cu(ptO2)(for)(H2O)] (4), [Cu(ptO2)(benz)]·H2O (5) (benz = benzoate), and [Cu(ptO2)F(H2O)]2·3H2O (6). This report includes the chemical and spectroscopic characterization of all these complexes along with the crystal structures of 4–6. The coordination spheres of CuII in 4 and 5 are best described as distorted tetragonal square pyramid…

Studies on metal-drug complexes. Crystal structure and characterization of μ-sulfato bromazepam copper(II) complex

Abstract The compound Cu(Bromazepam) SO 4 having been synthesized, its crystal structure shows distorted octahedral environment for the Copper(II) ion. Because of the long Cu-O(4) length (2.90 A), we can consider that there is a semicoordinative interaction with the sulfate group acting as tridentate bridging ligand. The structure is a polymeric chain where dimeric units are linked by the oxygen (C-O(5)) atom of the Bromazepam carbonyl group. The drug consequently acts as a tridentate ligand in this compound. The magnetic results show a very weak antiferromagnetic interaction.

Metal complexes of phenobarbituric acid. Chelating behavior of the phenobarbiturate ring. Anticonvulsant properties of the K2[Cu(N-methylphenobarbiturato)]4.8H2O.

Abstract Na2Ni(phenobarbiturato)4·3H2O, Na2Ni3(phenobarbiturato)2(OH)6·4H2O, and NaZn(phenobarbiturato)2(OH)·H2O derivatives were prepared from Ni(II) and Zn(II) and phenobarbital. The Na2Ni(phenobarbiturato)4·3H2O complex is diamagnetic and isostructural with the complex previously reported, Na2Cu(phenobarbiturato)4, suggesting a square-planar environment around the Ni(II) ion. The DMF solutions of this complex show the existence of two species. The EPR spectra of the Cu(II) doped complex show the hyperfine and superhyperfine structures. The covalence parameters α2, β2, and δ2 show a strong bonding in the equatorial plane and suggests the formation of a [CuN4] chromophore. The anticonvulsa…

New sulfonamide complexes with essential metal ions [Cu (II), Co (II), Ni (II) and Zn (II)]. Effect of the geometry and the metal ion on DNA binding and nuclease activity. BSA protein interaction.

Abstract Mixed divalent Cu, Co, Ni and Zn complexes containing the new sulfonamide ligand N–(2–(pyridin–2–yl)ethyl)quinoline–8–sulfonamide (HQSEP) were prepared and characterized by physico-chemical techniques. The tetracoordinate [Cu(QSEP)X] [X = Br (1), Cl (2)] compounds present a seesaw geometry (τ4 = 0.56 (1) and 0.50 (2)). The Cu(II) in the [Cu(QSEP)(NO3)(MeOH)] (3) complex is five coordinate with a slightly distorted SP geometry (τ = 0.11). The [M(QSEP)(benz)] [M = Cu(II) (4), Ni(II) (5), Co(II) (6) and Zn(II) (7); benz = benzoate] compounds are configurationally isotypic. The coordination geometries of the M(II) ions can be best described as distorted SP (τ = 0.29, 0.15, 0.34 and 0.1…

Complexes of 4-methoxy-2-(5-methoxy-3-methyl-pyrazol-1-yl)-6-methylpyrimidine, an anti-inflammatory agent—I. Copper(II) perchlorate complexes

Abstract The preparation and properties of copper(II) complexes of 4-methoxy-2-(4-methoxy-3-methyl-pyrazol-1-yl)-6-methylpyrimidine, are reported. Complexes of

Strong protective action of Copper(II) N-substituted sulfonamide complexes against reactive oxygen species.

Copper(II) complexes of N -benzothiazolsulfonamides, [Cu( N -2-(5,6-dimethylbenzothiazole)toluenesulfonamidate) 2 (dmso) 2 ] ( 1 ), [Cu( N -2-(6-chlorobenzothiazole)benzenesulfonamidate) 2 (dmso) 2 ] ( 2 ) and [Cu( N -2-(6-chlorobenzothiazole)toluenesulfonamidate) 2 (dmso) 2 ] ( 3 ) with interesting protective properties against superoxide radicals have been prepared. The compounds have been characterized by X-ray diffraction and their chemical properties have been studied by spectroscopic methods. The crystal structure of 1 shows that the copper(II) is surrounded by two benzothiazole N atoms from the sulfonamide ligands and two O atoms from the dimethylsulfoxide molecules in a square plana…

Biological Activity of Flavonoids Copper Complexes

Three flavonoid copper(II) complexes Cu2(quercetin)(CH3COO)3(CH3OH) (1), Cu(anthrarufin)(CH3COO)·1/2H2O (2) and Cu(naringin)(OCH3)(CH3OH)2 (3) have been synthesized and characterized by elemental analysis, IR, electronic absorption and EPR (X-band) spectroscopy. The complexes have a strong protective action over the Δsod1 mutant of S. cerevisiae against reactive oxygen radicals generated by an external source of free radicals (H2O2 or the superoxide-generating, menadione). On the other hand, the complexes cleave DNA efficiently even in the absence of reducing agents. The main reactive oxygen species responsible for the DNA strand cleavage have been determined using radical scavengers. A pro…

Syntheses, crystal structures, and oxidative DNA cleavage of some Cu(II) complexes of 5-amino-3-pyridin-2-yl-1,2,4-triazole

Three new monomeric Cu(II) complexes of 5-amino-3-pyridin-2-yl-1,2,4-triazole (Hapt), [Cu(Hapt)(H(2)O)(2)(SO(4))] (1), [Cu(Hapt)(2)(H(2)O)(NO(3))](NO(3)) (2), and [Cu(Hapt)(2)(NCS-N)](NCS).H(2)O (3), have been prepared and characterized by single crystal X-ray diffraction. One distorted [CuN(2)O(2)+O(')] square-pyramidal (1), one distorted [CuN(3)O+N(')+O(')] octahedral (2), and one distorted [CuN(4)+N(')] intermediate between square-pyramidal and trigonal-bipyramidal (3) coordination configuration were found and are suggested to be due to the chelating nature of the ligand, which interacts with Cu(II) through the N4(triazole) and N(pyridine) atoms. Spectral properties of these chelates are…

Copper-mediated DNA photocleavage by a tetrapyridoacridine (tpac) ligand.

Abstract We have focused our interest on the tetrapyridoacridine ligand tetrapyrido[3,2- a :2′,3′- c :3′′,2″- h : 2‴,3‴- j ]acridine (tpac), as a model system for the preparation of novel copper-based artificial nucleases. The complex of copper(II)–tpac cleaves supercoiled pUC18 plasmid DNA in an oxidative manner by photoactivation with visible light, exhibiting maximum cleaving efficiency at 1:2 metal–ligand stoichiometric ratio. We propose an interaction of the copper–tpac complex with DNA through both major and minor grooves and a photocleavage mechanism via the formation of hydroxyl radicals and singlet oxygen or singlet oxygen-like species.

Structure, magnetic properties and nuclease activity of pyridine-2-carbaldehyde thiosemicarbazonecopper(II) complexes.

New complexes of formulae [Cu(HL 2 )(H 2 O)(NO 3 )](NO 3 ) ( 1 ), [{Cu(L 1 )(tfa)} 2 ] ( 2 ), [{Cu(L 1 )} 2 (pz)](ClO 4 ) 2 ( 3 ) and {[{Cu(L 1 )} 2 (dca)](ClO 4 )} n ( 4 ), where HL 1  = pyridine-2-carbaldehyde thiosemicarbazone, HL 2  = pyridine-2-carbaldehyde 4 N -methylthiosemicarbazone, Htfa = trifluoroacetic acid (CF 3 COOH), pz = pyrazine (C 4 H 4 N 2 ) and dca = dicyanamide [N(CN) 2 ] − , have been synthesized and characterized. The crystal structures of these compounds are built up of monomers ( 1 ), dinuclear entities with the metal centers bridged through the non-thiosemicarbazone coligand ( 2 and 3 ) and 1D chains of dimers ( 4 ). In all the cases, square–pyramidal copper(II) io…

A Co(III) complex of carbonic anhydrase inhibitor methazolamide and the amino-imino ‘aib’ ligand formed by reaction of acetone and ammonia

Abstract Reaction of Co(NO 3 ) 2 ·6H 2 O with methazolamide {[ N -(3-methyl-5-sulfamoyl-1,3,4-thiadiazol-2(3 H )-ylidene)acetamide] (Hmacm)} and ammonia in acetone to produce [Co(methazolamidate)(2-methyl-2-amino-4-iminopentane) 2 (NH 3 )](NO 3 ) 2 ·2H 2 O is described. The ligand 2-methyl-2-amino-4-iminopentane (aib) is the product obtained from the condensation of two ammonia and two acetone molecules. The complex crystallizes in the monoclinic space group P 2 1 / c with a =16.713(5), b =9.180(1), c =20.273(1) A, β=97.44(4)° for Z =4. The R value is 0.081 for 2150 significant reflections. The Co(III) ion exhibits a nearly regular octahedral arrangement with the CoN bond distances in the …

Nuclease activity of [Cu(sulfathiazolato)2(benzimidazole)2]2MeOH. Synthesis, properties and crystal structure

The [Cu(sulfathiazolato)(2)(benzimidazole)(2)]2MeOH complex has been synthesised and characterised. It crystallises in the monoclinic system, space group C1c1, with unit cell dimensions a=18.829(7) A, b=12.206(3) A, c=17.233(5) A, alpha=90.06(2) degrees, beta=97.28(3) degrees, gamma=90.21(3) degrees and Z=4. The geometry around the copper(II) ion is intermediate between tetrahedral and square planar. The complex produces cleavage of plasmid pUC18 in presence of reducing agents. The efficiency of cleavage reaction of the title compound with pUC18 and with different reducing agents follows the order ascorbate-H(2)O(2)>ascorbate>MPA>dithiothreitol>H(2)O(2).

Revisiting the thiosemicarbazonecopper(II) reaction with glutathione. Activity against colorectal carcinoma cell lines.

Thiosemicarbazones (TSCs), and their copper derivatives, have been extensively studied mainly due to the potential applications as antitumor compounds. A part of the biological activity of the TSC-CuII complexes rests on their reactivity against cell reductants, as glutathione (GSH). The present paper describes the structure of the [Cu(PTSC)(ONO2)]n compound (1) (HPTSC =pyridine-2-carbaldehyde thiosemicarbazone) and its spectroscopic and magnetic properties. ESI studies performed on the reaction of GSH with 1 and the analogous [{Cu (PTSC*)(ONO2)}2] derivative (2, HPTSC* =pyridine-2-carbaldehyde 4N-methylthiosemicarbazone) show the absence of peaks related with TSC-Cu-GSH species. However GS…

Crystal structure, magnetic and spectroscopic properties of copper(II) formato dimethylformamide: a new tetracarboxylato-bridged copper(II) dimer

Abstract The crystal and molecular structure of a new tetracarboxylato copper(II) dimer [bis(dimethylformamide)tetrakis(μ-formato)dicopper(II)], has been determined by X-ray diffraction methods. The crystal structure consists of a centrosymmetric dimer [Cu2(HCOO)4(dmf)2], where four bidentate formato anions form syn–syn bridges between the metal ions which are in a 4+1 environment. Magnetic susceptibility data show that the copper ions are strongly antiferromagnetically coupled with J=−470 cm−1. The EPR spectrum shows a characteristic pattern of a triplet state with a D zero field splitting value of 0.27 cm−1.

Acetazolamide-M(II) [M(II) = Co(II), Ni(II), Cu(II)] complexes with ethylamine, diethylamine, triethylamine, and potassium hidroxide

Abstract Complexes of Co(II), Ni(II), and Cu(II) with dideprotonated Acm are synthesized and characterized. Acm acts as bidentate ligand through the N-sulfonamido atom and the N-thiadiazole atom except for K6CoAcm4·6H2O in which Acm behaves as monodentate through the N-sulfonamido atom.

In vivo and in vitro anti-leishmanial activities of 4-nitro-N-pyrimidin- and N-pyrazin-2-ylbenzenesulfonamides, and N2-(4-nitrophenyl)-N1-propylglycinamide.

A series of compounds containing the nitrobenzene and sulfonamido moieties were synthesized and their leishmanicidal effect was assessed in vitro against Leishmania infantum promastigotes. Among the compounds evaluated, the p-nitrobenzenesulfonamides 4Aa and 4Ba, and the p-nitroaniline 5 showed significant activity with a good selectivity index. In a Balb/c mice model of L. Infantum, administration of compounds 4Aa, 4Ba or 5 (5 mg/kg/day for 10 days, injected ip route) led to a clear-cut parasite burden reduction (ca. 99%). In an attempt to elucidate their mechanism of action, the DNA interaction of 4Aa and 5 was investigated by means of viscosity studies, thermal denaturation and nuclease …

Synthesis and copper-mediated nuclease activity of a tetracationic tris(2,2′-bipyridine) ligand

Abstract We report herein the synthesis of a novel tetracationic tris(2,2′-bipyridine) ligand 4 . We show that this ligand metalated with copper(II), and in the presence of ascorbate as a reducing agent, strongly damages pUC18 plasmid DNA. Copper complex formation was demonstrated by ESI-MS (electrospray ionization-mass spectrum) at a 1:3 ligand to metal ratio. Binding of both 4 and its copper(II) complex to CT-DNA (calf thymus DNA) was characterized by viscosimetry, thermal denaturation and fluorescence-based competition assays. The viscosimetric data indicated that 4 and its copper(II) complex bind DNA through partial intercalation and thermal denaturation studies revealed a significant i…

Coordination behaviour of methazolamide [N(-4-methyl-2-sulfamoyl-Δ2-1,3,4-thiadiazolin-5-ylidene)] acetamide, an inhibitor of carbonic anhydrase enzyme. Synthesis, crystal structure and properties of bis(methazolamidate)tetrammine nickel(II)

Abstract The interaction of methazolamide (Hmacm) with Ni(II) ion and ammonia molecules gives rise to the complex of formula [Ni(macm)2(NH3)4]. The complex crystallizes in the monoclinic P21/n space group with a = 14.255(4), b = 7.126(2), c = 12.444(3) A, β = 113.12(3)° and Z = 2. The structure was refined to R = 0.065 (Rw = 0.065). The complex consists of monomeric units which interact through hydrogen bonds and van der Waals contacts. The Ni(II) ion is coordinated with the deprotonated sulfonamido nitrogen of the macm− ligand in axial sites and the ammonia molecules in equatorial positions. IR, electronic spectra and 1H NMR results are also reported.

Antibiotic as Ligand. Coordinating Behavior of the Cephalexin Towards Zn(II) and Cd(II) Ions

The complex formation equilibria of Zn(II) and Cd(II) with cephalexin have been studied through potentiometric titrations. Experimental data were analyzed using the least squares computer program SUPERQUAD. The stability constants were 1g beta ZnCEX+ = 2.40, 1g beta Zn(CEX)(OH) = -4.54, 1g beta CdCEX+ = 2.18, and 1g beta Cd(CEX)(OH) = -5.18 (I = 0.1 M NaNO3), CEX complexes of formulae Zn(CEX)2(3)H2O and Cd(CEX)(OH)H2O have been synthesized and characterized by elemental analysis, IR spectra, conductivity measurements, and electronic and NMR spectra. The thermal behavior of the synthesized compounds were studied by TGA and DTA. We conclude that the metal ion interacts with the amido group of…

Oxidative DNA cleavage induced by an iron(III) flavonoid complex: synthesis, crystal structure and characterization of chlorobis(flavonolato)(methanol) iron(III) complex.

A flavonol iron(III) complex, [Fe(flavonolato)(2)Cl(MeOH)], has been prepared. The compound has been characterized by X-ray crystallography, spectroscopy, magnetism and electronic paramagnetic resonance (EPR) at X- and Q-band. The geometrical environment around the metal is best described as rhombic distorted octahedral. This distortion has also been inferred from the magnetic measurements and from the EPR spectra at different temperatures, E/D(rhombicity parameter) approximately 0.06. The DNA cleavage activity of the iron(III) complex with and without ascorbate/hydrogen peroxide is reported. Mechanisms of the oxidative cleavage have been proposed when DNA strand scission is performed both …

Complexes of Co(II) and Zn(II) with ofloxacin. Crystal structure of [Co(oflo)2(MeOH)2].4MeOH.

Abstract Ofloxacin (oflo) is able to interact with Co(II) and Zn(II) salts to form complexes with the general formula [M(oflo) 2 ] · 4H 2 O, (M = Co, Zn). Bonding takes place through one of the oxygen atoms of the carboxylate group (acting as a monodentate) and the oxygen atom of the ketonic group. The IR bands of the carboxylic and ketonic group at 1713 and 1622 cm −1 , respectively, shift to 1615 and 1575 cm −1 in the complexes. After dissolution in methanol, complex [Co(oflo) 2 ] · 4H 2 O crystallizes as [Co(oflo) 2 (MeOH) 2 ] · 4MeOH, where Co(II) ion is in an octahedral environment of oxygen atoms. This compound crystallizes in the triclinic system, spatial group P‐1, with unit cell di…

Coordination compounds of methazolamide. Synthesis, spectroscopic studies and crystal structures of [M(Methazolamidato)2(py)2(OH2)2] (M  CoII, NiII and CuII)

Abstract The synthesis and X-ray crystallographic characterization of three monomeric transition-metal coordination compounds with the ligand methazolamide {[N(4-methyl-2- sulphamoyl-Δ21,3,4-thiodiazolin-5-ylidene)],acetamide} (abbreviated as Hmacm) are described, via [M(macm)2(py)2(OH2)2] [M  Co(1), Ni(2) and Cu(3)]. In all the compounds the metal ion, lying on the centre of symmetry, is surrounded by two sulphonamidato nitrogen atoms and two pyridine nitrogen atoms in equatorial sites and two oxygen water molecules in axial positions. The coordination geometry of the metal is an almost regular octahedron around the cobalt(II) and nickel(II) ions. In contrast, the copper(II) ion has a sig…

Strong Ferromagnetic Coupling in Linear Mixed μ-Acetato, μ-Hydroxo Trinuclear Copper(II) Complexes withN-sulfonamide derivatives − Synthesis, Structure, EPR and Magnetic Properties

One-dimensional metal-organic framework with unprecedented heptanuclear copper units.

The reaction of copper(II) sulfate, copper(II) chloride, 3,5-diacetylamino-1,2,4-triazole, and 3-acetylamino-5-amino-1,2,4-triazole in water yields green, plate-shaped crystals of [[{Cu3(mu3-OH(1/2))L(H2O)2Cl}2{mu-Cu(H2O)2Cl2}].12H2O]n (1), where L is a new triazole-derived macrocyclic ligand. The structure of 1 consists of heptanuclear (H)OCuII(3)-CuII-CuII(3)O(H) entities linked in pairs through symmetric mu3-O...H...O-mu3 hydrogen bonds to form a double-stranded one-dimensional network. A significant overall antiferromagnetic behavior has been observed for 1.

Copper complexes with dithiocarbamates derived from natural occurring amino acids. Crystal and molecular structure of [Cu(en)(EtOH)(H2O)3][Cu(dtc-pro)2]

Abstract Reaction of Cu(II) salts with dithiocarbamates derived from the amino acids asparagine, glutamine, serine, threonine and tyrosine leads to reduction of the metallic cation and formation of Cu(I) complexes, whereas reaction with proline dithiocarbamate takes place without reduction, leading to formation of a Cu(II) coordination compound. Simultaneous reaction of proline dithiocarbamate and ethylenediamine with Cu(II) leads to the formation of the mixed complex [Cu(en)(EtOH)(H2O)3][Cu(dtc-pro)2]. In the anion, the Cu(II) centre possesses a D2h local symmetry, coordinated by two bidentate dithiocarbamate ligands, while the Cu(II) centre is in a distorted octahedral coordination in the…

Complex formation equilibria between the acetazolamide ((5-acetamido-1,3,4-thiadiazole)-2-sulphonamide), a potent inhibitor of carbonicanhydrase, and Zn(II),Co(II), Ni(II) and Cu(II) in aqueous and ethanol-aqueous solutions

Abstract The stability constants for the equilibrium of complexation between acetazolamide and the divalent metal ions copper(II), nickel(II), zinc(II), and cobalt(II) have been determined by potentiometry both in water and in water-ethanol 50 vol. % solutions in 0.15 mol dm −3 NaNO 3 at 25°C. This mixed solvent has been used in order to obtain higher concentrations of acetazolamide in solution. For copper(II) and nickel(II), the binuclear species [Cu 2 (Acm) 2 ] and [Ni 2 (Acm) 3 ] 2− are detected in both solvents together with hydroxo species. The values of the stability constants are always higher in the mixed solvent than in water. For cobalt(II) and zinc(II), while in aqueous solution …

Coordinative versatility of the carbonic anhydrase inhibitor benzolamide in zinc and copper model compounds

New benzolamide (H 2 bz, 5-phenylsulfonamide-1,3,4-thiadiazole-2-sulfonamide) zinc(II) and copper(II) complexes with tris(2-benzimidazolyl-methylamine) (L) and ammonia are reported. The crystal structures of the Zn(II) complexes were determined. The [Zn(Hbz)L]ClO 4 · H 2 O compound crystallizes in the triclinic space group with a =11.006(1), b =14.777(2), c =14.918(2) A, α =114.30(1), β =98.90(1), γ =107.36(1)° and Z =2. In this compound the Zn(II) has a distorted trigonal bipyramidal geometry. The {[Zn 2 (bz) 2 (NH 3 ) 4 ] · 2H 2 O} ∞ crystallizes in the monoclinic space group C 2/ c with a =23.530(3), b =10.4124(11), c =15.428(2) A, β =110.591(9)° and Z =4. The metal centre is in a distor…

ChemInform Abstract: Synthesis and Characterization of the Acetazolamide Complexes of Co(II) and Zn(II).

Abstract The preparation and characterization of the complexes of Acetazolamide (Acm) with Co(II) and Zn(II) are described. The complexes are of the type M(Acm) 2 (NH 3 ) 2 . Monodentate or bidentate behaviour of Acm from the electronic properties and the IR spectral data is discussed. The probable structures of the complexes are proposed.

Spectroscopic, magnetic, and electrochemical studies of a dimeric N-substituted-sulfanilamide copper(II) complex. X-ray and molecular structure of the Cu2(N-(pyridin-2-yl)biphenyl-4-sulfonamidate)4 complex

Abstract A dinuclear copper(II) complex with a N-substituted sulfonamide as ligand has been investigated. The new N-(pyridin-2-yl)biphenyl-4-sulfonamide ligand has been prepared and structurally characterized. The copper(II) complex has been synthesized and its crystal structure, magnetic properties and EPR spectra were studied in detail. The metal centers are bridged by four nonlinear triatomic NCN groups. The coordination geometry of the copper(II) ions in the dinuclear entity is distorted square planar with two N-pyridyl and two N-sulfonamido atoms. Magnetic susceptibility data show a moderate antiferromagnetic coupling, with −2 J = 284 cm−1. The EPR spectrum of the polycrystalline sampl…

Desulfurization processes of thiosemicarbazonecopper(ii) derivatives in acidic and basic aqueous media

This work provides structural evidence for different desulfurization processes in aqueous solutions of [CuL]+ derivatives (HL = pyridine-2-carbaldehyde thiosemicarbazone). Structural resolution has been achieved for the [{CuL(SH)}2] (1), [CuLCl]2[Cu(pic)2] (pic− = picolinato, pyridine-2-carboxilato) (2) and [Cu(HL)(NCS)](NO3) (4) compounds, together with a derivative of 4 with formula [Cu(HL)(NCS)][Cu(HL)(NCS)0.72(NO3)0.28](NO3)2 (5), whose HS−, pic− and NCS− ligands come from thiosemicarbazone breakage. The behaviour of the [CuL]+ species in basic aqueous solutions or water under reflux has been compared with that exhibited by iron(III), cobalt(III), zinc(II) and lead(II) derivatives of th…

SEVERAL COORDINATION MODES OF 5-AMINO-1,3,4-THIADIAZOLE-2-SULFONAMIDE (HATS) WITH Cu(II), Ni(II) AND Zn(II): MIMETIC TERNARY COMPLEXES OF CARBONIC ANHYDRASE-INHIBITOR

Abstract The coordination properties of 5-amino-1,3,4-thiadiazole-2-sulfonamide (Hats) with Cu(II), Ni(II) and Zn(II) ions, are analyzed. Although the ligand presents several donor atoms, we have only observed three coordination behaviors: (i) as a monodentate ligand through the Nsulfonamido atom, (ii) as a bridging ligand linking the metal ions through the Nsulfonamido and Nthiadizole atoms and (iii) as a bridging ligand linking metal ions through the N and O atoms of the sulfonamidate group. It is noteworthy that coordination mode (iii) is observed for the first time in heterocyclic sulfonamides complexes. In addition, the conformation of the Hats as counter-ion is analyzed and compared w…

Thermal studies of sulphonamide derivative complexes

Abstract A thermal study of a new series of acetazolamidate complexes of Co(II), Ni(II) and Cu(II) using the TG, DTG and DTA techniques in flowing air, static air and N 2 atmospheres is described. From the TG-DTG and DTA curves, different thermal behaviours can be observed. Although in all the complexes the processes of dehydration, deammination and pyrolysis can be clearly observed, in some cases they appear as several well-separated steps and, in others, as continuous stages which take place simultaneously. The differences observed between the pyrolytic decomposition in flowing air and in nitrogen are described. In flowing air, metal sulphate is formed from the thiadiazole ring, except fo…

Zinc complexation to N-substituted sulfonamide ligands. Preparation, properties and crystal structure of copper(II) doped ?[Zn(sulfamethizolate)2(py)]·H2O?∞

Abstract The single crystal structure and spectroscopic properties of the copper(II) doped {[Zn(sulfamethizolate) 2 (py)]·H 2 O} ∞ are reported. The complex is a polymer where the Zn(II) ions are coordinated by four N atoms in a very distorted tetrahedral environment. The sulfamethizolate anion acts as a monodentate ligand through the thiadiazole N atom and as a bridging ligand via the amino and thiadiazole N atoms. The compound is studied by EPR, by 13 C NMR in solid state and by 1 H and 13 C NMR in DMSO-d 6 solution. The similarity between the 13 C NMR spectrum in solution and the solid 13 C NMR spectrum indicates that the structure of the compound remains in solution. The EPR spectrum sh…

Comparison of Protective Effects against Reactive Oxygen Species of Mononuclear and Dinuclear Cu(II) Complexes with N-Substituted Benzothiazolesulfonamides

Copper(II) complexes of N-benzothiazolesulfonamides (HL1=N-2-(4-methylphenylsulfamoyl)-6-nitro-benzothiazole, HL2=N-2-(phenylsulfamoyl)-6-chloro-benzothiazole, and HL3=N-2-(4-methylphenylsulfamoyl)-6-chloro-benzothiazole) with ammonia have been synthesized and characterized. The crystal structures of the [Cu(L1)2(NH3)2].2MeOH, [Cu(L2)2(NH3)2], and [Cu(L3)2(NH3)2] compounds have been determined. Compounds and present a distorted square planar geometry. In both compounds the metal ion is coordinated by two benzothiazole N atoms from two sulfonamidate anions and two NH3 molecules. Complex is distorted square-pyramidal. The Cu(II) ion is linked to the benzothiazole N and sulfonamidate O atoms o…

Three-Dimensional Mixed-Ligand Coordination Polymers with Ferromagnetically Coupled Cyclic Tetranuclear Copper(II) Units Bonded by Weak Interactions

The complexes {[Cu(HGLYO)(NO3)(bpy)]·H2O}4 (1), {[Cu(HGLYO)(NO3)(phen)]·H2O}4 (2), and [Cu(HLACO)(ClO4)(phen)]4 (3) (bpy is 2,2′-bipyridine, phen is 1,10-phenanthroline, HGLYO is monoanionic glycol...

(1,3,4‐Oxadiazole)copper(II) Compounds: Dimensionality, Magnetism and Nuclease Activity

The work presented here describes the synthesis of new copper(II) complexes derived from 2-amino-5-(pyridin-2-yl)-1,3,4-oxadiazole (L1) and 2-methylamino-5-(pyridin-2-yl)-1,3,4-oxadiazole (L2) which also incorporate azido (N3 -), thiocyanato (NCS-), cyanato (NCO-), dicyanamido [N(CN)2 -, dca] and malonato (C3H2O4 2-, mal) coligands. Structures of the [Cu(L2)(mal)(H2O)]·2H 2O(1), [{Cu(L2)(mal)}2] (2), [Cu(L 2)2-(NCS)2] (3), [Cu(L1)(NCS) 2]n (4) and [{Cu(L2)}2(dca) 2](ClO4)2·2H2O (5) compounds show the dependence of the dimensionality on parameters such as the type of oxadiazole and coligand utilised, solvents or reaction times. In this sense, 1 and 3 are mononuclear complexes, 2 contains cen…

ChemInform Abstract: Ternary Complexes of Cimetidine and Phenobarbital with Cu(II) in Methanolic Solution.

The formation constants of the binary complexes Cu(CM)2+ and Cu(CM) 2 2+ as well as those of the ternary complexes Cu(CM)L + and Cu(CM)2 L + (CM=Cimetidine=N-Cyano-N′-methyl-N″[(5-methyl-1H-imidazol-4-yl)methyltioethyl]-guanidine; HL=Phenobarbital=5-ethyl-5-phenyl-barbituric acid) have been determined in 0.1 and 1.0 mol dm−3 NaClO4 methanol solutions at 25±0.2°C. The values of logX, log βstat.., and Δ logK confirm the stability of the ternary complexes.

Metal complexes of anxiolitic drugs. X-Ray crystal structure and electronic properties of aquobromazepam(oxalato O1 O2) copper(II)

The crystal structure of the title compound has been determined from single-crystal x-ray diffraction data. The copper(II) ion is surrounded by two nitrogen atoms of the bromazepam** molecule [N(imine) and N(pyridine)], and two oxygen atoms of the oxalate ion in a square planar arrangement. One molecule of water is linked to the copper(II) ion in the axial position. The complex has been also characterized by electronic, e.s.r. and i.r. spectra.

Synthesis, properties and crystal structure of an N-cyano-N′-methyl-N″-[2-{(5-methyl-1H-imidazol-4-yl)-methylthio}ethyl]guanidi

Abstract A Cu(II) complex has been prepared with N-cyano-N′-methyl-N′'-[2-{(5-methyl-1H-imidazol-4-yl)-methylthio}ethyl]guanidine, cimet

Synthesis and characterization of acetazolamide complexes of Ni(II), Cd(II), Hg(II), and Ag(I)

The preparation and characterization of K2Ni2(Acm)3·5H2O, Cd(Acm)·32 H2O, Hg(Acm)·12H2O, Ag2(Acm), and Ag2(Acm)(NH3) complexes are described. The spectral properties suggest that Acm interacts with the metal ions through the doubly deprotonated form as observed in the [Cu(Acm)(NH3)2(OH2)]2·2H2O complex, whose crystalline structure has been previously reported. The crystal field parameters of the Ni(II) complex indicate an octahedral environment for the metal ion in the solid and its aqueous, DMSO, and DMF solutions. UV spectra of all the Acm complexes until now synthesized are discussed.

Coordination behaviour of sulfanilamide derivatives.

Abstract Hg(II), Cd(II) and Zn(II) complexes with the ligands sulfadimethoxine, sulfamethoxypyridazine, sulfadiazine, sulfamerazine, sulfadimidine and sulfamethoxazole have been prepared and characterised by spectral data. 1H and 13C NMR have been used to interpret the structural characteristics of the complexes in solution. The X-ray crystal structures of [Hg(sulfamethoxypyridazinato)2] (2a), [Cd(sulfadimidinato)2(H2O)]·2H2O (4b) and [Zn(sulfamethoxazolato)2(py)2(H2O)2] (6d) have been determined. In complex 2a the Hg(II) ion lies on an inversion centre and exhibits linear coordination by two sulfonamidic nitrogen atoms [Hg–N(1)=2.071(4) A] of the two deprotonated sulfamethoxypyridazinato l…

Spectroscopic behaviour of metal–drug complexes. Infrared spectra of Cu(II) complexes with 5-amino-1,3,4-thiadiazole-2-thiol (Hatm)

Abstract The infrared spectra of the drug Hatm and its copper (II) complexes with stoichiometry [Cu(atm) 2 (H 2 O)] and [Cu(Hatm)(HIm) 2 (SO 4 )] are reported and discussed. The Raman spectrum of Hatm is also reported. An assignment of Hatm, HIm, H 2 O and SO 4 modes in the complexes is proposed in comparison with the modes of the free ligands. Important information about the metal–ligand vibrations has been obtained.

Coordination chemistry of sulfamethizole: crystal structures of [Cu(sulfamethizolate)2(py)2(OH2)]·H2O, [M(sulfamethizolate)2(py)2(OH2)2] [M=Co and Ni] and {Cu(sulfamethizolate)2(dmf)2}∞

Abstract The synthesis and characterisation of copper, cobalt, nickel and zinc compounds with sulfamethizole (4-amino-N-(5-methyl-1,3,4-thiadiazole-2-yl)sulfanilamide) (Hsmtz) are described. The first crystal structures of ternary sulfamethizole complexes are reported. The crystal structures of Cu(smtz)2(py)2(OH2)·H2O (1), M(smtz)2(py)2(OH2)2 [M=Co (2), Ni (3)] and {Cu(smtz)2(dmf)2}∞ (5) were determined by X-ray diffraction. The Cu(II) ion exhibits a square pyramidal geometry in complex 1, while in the other compounds the metal ion presents a distorted octahedral environment. In compounds 1, 2 and 3 the deprotonated sulfamethizole acts as monodentate ligand coordinating through the thiadiaz…

Copper complexes modelling the interaction between benzolamide and Cu-substituted carbonic anhydrase. Crystal structure of Cu(bz)(NH3)4 complex

New copper benzolamide (H 2 bz, 5-phenylsulfonamide-1,3,4-thiadiazole-2-sulfonamide) complexes with ammonia, diethylentriamine (dien) and dipropylentriamine (dipn) have been prepared. The complex [Cu(bz)(NH 3 ) 4 ] crystallises in the monoclinic space group P 2 1 / n with a = 7.621(3), b = 19.91(5), c = 11.291(3) A, β = 93.17(4)° and Z = 4. The Cu(II) is five-coordinated with an almost regular square pyramidal geometry. The dideprotonated sulfonamide behaves as monodentate ligand interacting with the metal ion through the N atom of the unsubstituted sulfonamide group. In the EPR spectrum, exchange coupling between Cu(II) polyhedra of different orientations in the unit cell is observed. The …

Influence of tetrahedral distortion of CuN4 complexes on spectroscopic properties. Synthesis, characterization and crystal structures of [Cu(N-(2-methylpyridyl)benzenesulfonylamidate)2], [Cu(N-(2-methylpyridyl)toluenesulfonylamidate)2] and [Cu(N-(2-methylpyridyl)naphthalenesulfonylamidate)2] compounds

Abstract A series of new N-sulfonamide ligands and their copper(II) complexes, [Cu(N-(2-methylpyridyl)toluenesulfonylamidate)2] (1), [Cu(N-(2-methylpyridyl)benzenesulfonylamidate)2] (2) and [Cu(N-(2-methylpyridyl)naphthalenesulfonylamidate)2] (3), have been synthesized and characterized. Single crystal X-ray analysis of the three complexes revealed that all of them present a tetracoordinate CuN4 chromophore. The ligands act as bidentate, coordinating the metal ion through the pyridine and sulfonamido N atoms. The main structural difference among the compounds is the varied degree of distortion of square-planar stereochemistry. Complex 1 exhibits a regular square-planar geometry. In complexe…

Spectroscopic behavior of metal–drug complexes. Infrared spectra of Cu(II) dimer complexes with acetazolamide (H2acm) and an analogue sulfonamide (B-H2ats)

Abstract The infrared spectra of the drugs H2acm and B-H2ats, and their copper(II) dimer complexes with stoichiometries [Cu(acm)(NH3)2(OH2)]2·H2O and [Cu(B-ats)(NH3)2]2 are reported and discussed. The Raman spectra of H2acm and B-H2ats are also reported. An assignment of H2acm and B-H2ats modes in the complexes is proposed in comparison with the modes of the free ligands. The spectral modifications due to the deprotonation and coordination effects are analyzed. The ν(N–H) modes of the sulfonamido, carbonamido and Nring–H of the imine tautomer have been accurately assigned. Important information about the S–O and S–N vibrations has been obtained.

Coordination behavior of sulfathiazole. Crystal structure of [Cu (sulfathiazole) (py)3Cl] superoxide dismutase activity

Abstract The preparation, spectroscopic, magnetic properties, and crystal structure of [Cu(stzxpy) 3 Cl] (stz − stands for the deprotonated form of sulfathiazole, 4-amino-N-2-thiazolylbencenosulfonamide) are reported. Crystals are orthorhombic, space group Pbca, with cell constants a = 15.834(2), b = 17.512(4), and c = 18.79(2) A, and Z = 8. The structure was solved and refined to R = 0.041 (R W = 0.040). The structure consists of mononuclear units linked via hydrogen bonds to form the tridimensional pyramid. The geometry of CuN3N*NCl chromophore is distorted square-pyramid. The superoxide-dismutase mimetic activity of the compound is measured and compared with those of the SOD enzyme, the …

Cimetidine complexes derived from cobalt(II), nickel(II) and copper(II) salts of polyatomic anions

Cobalt(II), nickel(II) and copper(II) complexes [M(CM)2]X2 (X = BF4 or NO3) have been prepared with cimetidine (CM). Powder data, molar conductivities, magnetic moments, i.r. and electronic spectra support apseudo-octahedral stereochemistry with MN2N 2 ⋆ S2 chromophore and tentative structures are proposed for the complexes. Their properties are compared with these of previously prepared complexes.

Synthesis and characterization of the acetazolamide complexes of Co(II) and Zn(II)

Abstract The preparation and characterization of the complexes of Acetazolamide (Acm) with Co(II) and Zn(II) are described. The complexes are of the type M(Acm) 2 (NH 3 ) 2 . Monodentate or bidentate behaviour of Acm from the electronic properties and the IR spectral data is discussed. The probable structures of the complexes are proposed.

Countercomplementarity and Strong Ferromagnetic Coupling in a Linear Mixed μ-Acetato, μ-Hydroxo Trinuclear Copper(II) Complex. Synthesis, Structure, Magnetic Properties, EPR, and Theoretical Studies

The structural and magnetic data of the trinuclear compound [Cu3(L)2(CH3COO)2(OH)2(dmf)2] (HL = N-(2-methylpyridyl)toluensulfonylamide) are reported. The compound crystallizes in the monoclinic system, space group P2(1)/n (no. 14), with a = 11.6482(6) A, b = 13.5772(6) A, c = 13.5306(7) A, alpha = 90 degrees, beta = 92.859(5) degrees, gamma = 90 degrees, and Z = 2. The three copper atoms form an exact linear arrangement. Neighboring coppers are connected by a hydroxo bridge and a bidentate syn-syn carboxylato group. The coordination spheres of the terminal copper atoms are square pyramidal with a dmf molecule as the apical ligand. The central copper has a regular square planar geometry. The…

Complexes of Ni(II) and Cu(II) with ofloxacin. Crystal structure of a new Cu(II) ofloxacin complex.

Several coordination compounds formed between Ni(II) or Cu(II) with ofloxacin have been synthesised and characterised. According to elemental chemical analysis and FT-IR spectroscopy data, direct reaction of Ni(II) and Cu(II) salts with ofloxacin leads to formation of precipitates for which mass spectrometry demonstrates their polymeric nature. However, crystalline [Cu(oflo)2(H2O)].2H2O is formed if the reaction is carried out in the presence of ammonia. This complex crystallises in the triclinic system, space group P-1 with a=9.2887(12), b=11.2376(14), c=17.874(2) A, alpha=92.12(3), beta=95.39(3), gamma=91.71(3) degrees and Z=2. The local geometry around the Cu(II) ion is a slightly distor…

Spectroscopic, Magnetic, and Electrochemical Studies of a Dimeric N-Substituted-Sulfanilamide Copper(II) Complex. X-ray and Molecular Structure of the Cu(2)(sulfathiazolato)(4) Complex.

A copper(II) complex of formula Cu(2)(stz)(4) (stz(-) = sulfathiazolato) has been synthesized and characterized by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic system, space group P2(1)cn with a = 10.595(7) Å, b = 14.274(3) Å, c = 29.65(1) Å, and Z = 4. The structure consists of dinuclear copper(II) units which contain four sulfathiazolato ligands bridging the metal ions through a nonlinear NCN group. The copper atoms are four-coordinated, the chromophore being CuN(4). The Cu.Cu bond distance is 2.671(2) Å. Magnetic susceptibility data in the temperature range 7-300 K show the occurrence of intramolecular antiferromagnetic coupling with 2J = -61.5 cm(-1). …

Genotoxic Potential of N ‐(Benzothiazolyl)sulfonamide Copper(II) Complexes on Yeast Cells Transformed with YEGFP Expression Constructs Containing the RAD54 or RNR2 Promoter

Four ternary complexes [Cu(L)2(phen)] where L is an N(benzothiazol-2-yl)sulfonamide derivative have been prepared and their ability to cleave DNA has been studied. The complexes were structurally characterized with the aid of single-crystal X-ray crystallography. Whereas the molecular structure of the [Cu(L1)2(phen)] (1) [HL1 = N-(6-chlorobenzothiazol-2-yl)benzenesulfonamide] and [Cu(L3)2(phen)] (3) [HL3 = N-(benzothiazol-2-yl)benzenesulfonamide] complexes can best be described as having a distorted squareplanar geometry, that of the [Cu(L4)2(phen)] (4) [HL4 = N(benzothiazol-2-yl)toluenesulfonamide] complex shows a strictly square-planar geometry. The [Cu(L2)2(phen)MeOH] (2) [HL2 = N-(6-chl…

Oxidative DNA damage of mixed copper(II) complexes with sulfonamides and 1,10-phenanthroline

Abstract Mixed coordination compounds of Cu(II) with sulfonamides and 1,10-phenanthroline as ligands have been prepared and characterised. Single crystal structural determination of the complex [Cu( N -quinolin-8-yl- p -toluenesulfonamidate) 2 (phen)] shows Cu(II) ions are located in a highly distorted octahedral environment, probably as a consequence of the Jahn–Teller effect. The FT-IR and electronic paramagnetic resonance (EPR) spectra are also discussed. The mixed complexes prepared undergo an extensive DNA cleavage in the presence of ascorbate and hydrogen peroxide. Two of the complexes have higher nucleolytic efficiency than the bis( o -phenanthroline)copper(II) complex.

Cu(II) complexes with a sulfonamide derived from benzoguanamine. Oxidative cleavage of DNA in the presence of H2O2 and ascorbate

Reaction between benzoguanamine (2,4-diamino-6-phenyl-1,3,5-triazine) and 2-mesitylenesulfonyl chloride leads to formation of a sulfonamide able to form two mononuclear Cu(II) complexes with a CuL(2) stoichiometry. The local environment of the metal cation is a distorted octahedron, with two ligands and two solvent molecules; both complexes crystallize in the monoclinic structure, space group P2(1), with Z=2. In the presence of ascorbate/H(2)O(2,) the two complexes significantly cleavage double-strand pUC18 DNA plasmid. Both complexes exhibit more nuclease efficiency that the copper phenantroline complex. From scavenging reactive oxygen studies we conclude that the hydroxyl radical and a si…

Copper complexes with sulfonamides: crystal structure and interaction with pUC18 plasmid and hydrogen peroxide

N-Quinolin-8-yl-benzenesulfonamide (Hqbsa) and N-quinolin-8-yl-naftalenesulfonamide (Hqnsa) have been synthetized and physicochemically characterized, and used as ligands to coordinate copper complexes with ML2 stoichiometry. The structure of the compounds [Cu(qbsa)2]·DMF and [Cu(qnsa)2] has been determined by X-ray diffraction and both of them crystallize in the orthorhombic system. IR and ESR spectra of the complexes are discussed. The cleavage of pUCI8 by the copper complexes do not behave as chemical nucleases in the range of concentrations assayed.

Copper(II) Complexes with Derivatives of Barbiturate

Abstract NaCuL2(OH).1,5H2O, KCuP2(OH).1H2O, Na2CuL4 and K2CuP4-8H2O (HL=Phenobarbitone and HP=Methyl Phenobarbitone) were prepared and characterized by elemental analysis, IR and electronic spectral data and magnetic susceptibility measurements. The ESR spectra show and octahedral environment for the Cu(II) ion.

Superoxide dismutase activity of ternary copper complexes of sulfathiazole and imidazole derivatives. Synthesis and properties of [CuL2(R-Him)2] [HL=4-amino-N-(thiazol-2-yl)benzenesulfonamide, R-Him=4-methylimidazole, 4,4-dimethylimidazoline or 1,2-dimethylimidazole]. Crystal structure of [CuL2(4,4-dimethylimidazoline)2]

Abstract New ternary copper(II) complexes of sulfathiazole (4-amino-N-(thiazol-2-yl)benzenesulfonamide)(HL) and methyl imidazole derivatives have been synthesised and characterised. The crystal structure of the complex [CuL2(4,4-dmHim)2] (1) [4,4-dmHim=4,4-dimethylimidazoline] has been determined. The copper centre has a quasi regular square planar environment with Cu-nitrogen bond lengths ranging from 1.952 to 2.010 A. From the spectroscopic properties of the complexes [CuL2(1,2-dmHim)2] (2) [1,2-dmHim=1,2-dimethylimidazole] and [CuL2(4-mHim)2] (3) [4-mHim=4-methylimidazole] a distorted tetragonal octahedral geometry is deduced. The compounds showed SOD mimetic activity in fact, a low conc…

Complex formation of hypoxanthine and 6-mercaptopurine with Cd(II) ion

Reaction of Cd(II) ion with hypoxanthine (H2 Y) and with 6-mercaptopurine (H2 MP) in dioxane-water (50%) leads to the formation of CdY·2H2O and Cd(HMP)2·2H2O, respectively. In methanolic medium Cd(II) and H2 MP give Cd(MP)·H2O. These compounds have been characterized by chemical analysis, IR spectra and thermogravimetric analysis. The stability constant of CdY complex at 25±0.1 °C and 1M ionic strength with NaClO4 in dioxane-water medium is log β=10.25±0.05.

Crystal structure and electronic properties of bis(mepirizole) copper(II) perchlorate. Correlation between the electronic spectrum and CuN4 chromophore distortion from tetrahedral symmetry

The crystal structure of the title compound has been determined from single-crystal x-ray diffraction data. The crystals are tetragonal, space group P42212, withz=2 in a unit cell of dimensionsa=b=9.575(2),c=16.135(5) A. The structure was solved by the usual Patterson and Fourier techniques, and was refined by least-squares analysis to an R value of 0.057 for 545 observed reflexions. Two mepirizole molecules are arranged in a flattened tetrahedral manner (average Cu-N, 1.974 A) around Cu, and coordinated through N atoms. The dihedral angle between N-Cu-N planes of the two ligands is 53.6+°. This geometry seems to result from steric interaction between the ligands. The e.s.r. spectrum is axi…

Toward the development of metal-based synthetic nucleases: DNA binding and oxidative DNA cleavage of a mixed copper(II) complex with N-(9H-purin-6-yl)benzenesulfonamide and 1,10-phenantroline. Antitumor activity in human Caco-2 cells and Jurkat T lymphocytes. Evaluation of p53 and Bcl-2 proteins in the apoptotic mechanism

Abstract The complex [Cu(N9-ABS)(phen) 2 ]·3.6H 2 O, H 2 N9-ABS  = N -(9 H -purin-6-yl)benzenesulfonamide and phen = 1,10-phenanthroline, has been synthesized and then characterized with the aid of X-ray diffraction, analytical, and spectroscopic techniques. The geometry of Cu(II) is distorted square pyramidal with the equatorial positions occupied by three N atoms from two phenantroline molecules and one N atom from the adenine ring of the sulfonamide ligand. The interaction of the complex with DNA was studied by means of viscosity measurements and fluorescence spectroscopy. The results pointed to a classic intercalation of the complex between the DNA base pairs. The complex was found to b…

Comparison of the interaction of cobalt bovine carbonic anhydrase II with acetazolamide and methazolamide and the reaction of apoenzyme with cobalt(II) complexes of acetazolamide and methazolamide: Spectrophotometric study

The metalloenzyme carbonic anhydrase (CA) is an attractive choice for a research-based bioinorganic laboratory course. In this project the interaction of cobalt bovine carbonic anhydrase II (CoBCAII) with acetazolamide and methazolamide and the reaction of apoenzyme with cobalt(II) complexes of acetazolamide and methazolamide is studied by UV-visible spectroscopy. Prior to this spectroscopic study students are given native BCAII, and they prepare apoBCAII and CoBCAII. A major aim is to provide experience in handling metalloproteins and in the study of metal complexes-protein interactions.

Metal complexes of sulfanilamide derivatives. Crystal structure of [Zn(sulfathiazole)2]·H2O

Abstract The crystal structure of the Zn(sulfathiazole) 2 ·H 2 O complex is reported. The complex crystallizes in the monoclinic space group C 2/ c . The cell dimensions are a = 9.098(3) A, b = 17.871(5) A, c = 14.61(1) A, β = 99.44(6)°, V = 2343(2) A 3 , Z = 4, and D x = 1.68 g/cm 3 . The final conventional R-factor = 0.027 for 2669 “observed” reflections and 191 variables. The Zn ion is surrounded in a regular tetrahedral arrangement by two N amino and two N thiazole atoms pertaining to four sulfathiazole (Hstz) ligands. Each stz anion, acting as a bidentate ligand, chelates to two Zn ions as a bridge through the N thiazole and the N amino atoms. The IR, 13 C NMR in solid state, 1 H NMR, …

Cobalt(II), nickel(II) and copper(II) complexes withN-cyano-N?-methyl-N?(2-[(5-methyl-1H-imidazol-4-yl)methylthio]ethyl)guanidine

N-Cyano-N′-methyl-N″(2-[(5-methyl-1H-imidazol-4-yl)-methylthio] ethyl) guanidine cimetidine (CM), complexes with CoII, NiII and CuII are described. The compounds are of stoichiometry [M(CM)2]SO4 · nH2O [M = CoII, NiII or CuII; n = 3,3 or 4, respectively], [M(CM)2](ClO4)2 [M = CoII or NiII], [M(CM)2]Cl2 · nH2O [M=CoII, NiII or CuII; n = 1, 2, or 2, respectively] and [Cu(CM)SO4] · 2H2O. The electronic spectra of the compounds in solid state, magnetic susceptibilities and i.r. and e.p.r. spectra were studied. Octahedral environments are proposed for the complexes: [M(CM)2]SO4·nH2O, [M(CM)2](ClO4)2, [Ni(CM)2]Cl2 · 2H2O, [Cu(CM)2]Cl2 · 2H2O and [Cu(CM)SO4] · 2H2O and a tetrahedral structure for …

Carbonic anhydrase inhibitors

Reaction of 20 aromatic/heterocyclic sulfonamides containing a free amino, imino, hydrazino or hydroxyl group, with 8-quinoline-sulfonyl chloride afforded a series of water-soluble (as hydrochloride or triflate salts) compounds. The new derivatives were assayed as inhibitors of the zinc enzyme carbonic anhydrase (CA), and more precisely of three of its isozymes, CA I, II (cytosolic forms) and IV (membrane-bound form), involved in important physiological processes. Efficient inhibition was observed against all three isozymes, but especially against CA II (in nanomolar range), which is the isozyme known to play a critical role in aqueous humor secretion within the ciliary processes of the eye…

Ternary complexes of cimetidine and phenobarbital with Cu(II) in methanolic solution

The formation constants of the binary complexes Cu(CM)2+ and Cu(CM) 2 2+ as well as those of the ternary complexes Cu(CM)L + and Cu(CM)2 L + (CM=Cimetidine=N-Cyano-N′-methyl-N″[(5-methyl-1H-imidazol-4-yl)methyltioethyl]-guanidine; HL=Phenobarbital=5-ethyl-5-phenyl-barbituric acid) have been determined in 0.1 and 1.0 mol dm−3 NaClO4 methanol solutions at 25±0.2°C. The values of logX, log βstat.., and Δ logK confirm the stability of the ternary complexes.

Coordinative Versatility of Guanazole [3,5‐Diamino‐1,2,4‐triazole]: Synthesis, Crystal Structure, EPR, and Magnetic Properties of a Dinuclear and a Linear Trinuclear Copper(II) Complex Containing Small Bridges and Triazole Ligands

New complexes with guanazole (3,5-diamino-1,2,4-triazole = Hdatrz), [Cu 2 (Hdatrz) 2 (μ-OH 2 )(H 2 O) 4 (SO 4 )](SO 4 )·3.5H 2 O (1) and [Cu 3 (Hdatrz) 4 (μ-Cl) 2 (H 2 O) 4 (SO 4 ) 2 ]·11.4H 2 O (2), have been prepared and structurally characterized. Complex 1 is a noncentrosymmetric dinuclear compound in which the cop-per(II) ions are bridged by two triazole ligands and one μ-OH 2 molecule, with a Cu(1)···Cu(2) distance of 3.4945(8) A. The chromophores are Cu(1)N 2 O 2 O' (square pyramidal), and Cu(2)N 2 O 2 O'O" (octahedral). Complex 2 has a linear trinuclear copper(II) structure, with two crystallographically independent copper(II) atoms. Neighboring copper(II) ions are linked by two tri…

Oxidative nuclease activity of ferromagnetically coupled μ-hydroxo-μ-propionato copper(II) complexes [Cu3(L)2(μ-OH)2(μ-propionato)2] (L=N-(pyrid-2-ylmethyl)R-sulfonamidato, R=benzene, toluene, naphthalene)

Three doubly-bridged, trinuclear copper(II) compounds with hydroxo and carboxylato bridges, ∞ 1 [Cu 3 (L1) 2 (μ-OH) 2 (μ-propionato) 2 ] ∞ 1 [ Cu 3 ( L 1 ) 2 ( μ - OH ) 2 ( μ - propionato ) 2 ] (1) , [Cu 3 (L2) 2 (μ-OH) 2 (μ-propionato) 2 (DMF) 2 ] (2) and ∞ 1 {[Cu 3 (L3) 2 (μ-OH) 2 (μ-propionato) 2 ]} ∞ 1 { [ Cu 3 ( L 3 ) 2 ( μ - OH ) 2 ( μ - propionato ) 2 ] } [Cu 3 (L3) 2 (μ-OH) 2 (μ-propionato) 2 (DMF) 2 ]} (3) [HL1 =  N -(pyrid-2-ylmethyl)benzenesulfonylamide, HL2 =  N -(pyrid-2-ylmethyl)toluenesulfonylamide, HL3 =  N -(pyrid-2-ylmethyl)naphthalenesulfonylamide], have been synthesized and characterized. 1 is built from [Cu 3 (L1) 2 (μ-OH) 2 (μ-propionato) 2 ] clusters. Each unit contai…

Copper Complexes with Sulfonamides Derivatives of Natural Amino Acids as Chemical Nucleases

Three new coordination compounds have been prepared by reacting copper salts with sulfonamides derived from amino acids. Their molecular structures have been determined with the aid of single crystal X-ray diffraction. The copper cations are four-coordinated in all cases and the local environment is almost planar. Compound [Cu(ts-gly)(NH3)2]·H2O (1) crystallizes in monoclinic space group P21/c (no 14) with Z = 4 and with unit cell parameters a = 6.0490(12) A, b = 24.719(5) A, c = 9.159(2) A, α = γ = 90°, and β = 94.69(3)°. Compound [Cu(ts-isoleu)(NH3)2] (2) crystallizes in monoclinic space group C2/c (no 8) with Z = 15 and with unit cell parameters a = 30.800(6) A, b = 6.5510(13) A, c = 15.…

Tetrakis[(mu-hydroxo)(mu-sulfathiazolato)copper(II)] tetrakis(dimethyl sulfoxide): a new square-planar tetranuclear copper(II) complex containing four hydroxo and four NCN-sulfathiazolato bridges. Electrochemical synthesis, crystal structure, and magnetic properties.

Synthesis, Characterization and Magnetic Properties of New Dinuclear Copper(II) Complexes with N,N′-Disubstituted Dithiooxamides derived from α-Amino Acids

Four new dinuclear copper(II) complexes have been synthesized and have the general formula [Cu2(L)(H2O)2], where L = GLYDTO [N,N′-bis(carboxymethyl)dithiooxamide], ALADTO [N,N′-bis(carboxyethyl)dithiooxamide], VALDTO [N,N′-bis(1-carboxy-2-methylpropyl)dithiooxamide] and LEUDTO [N,N′-bis(1-carboxy-3-methylbutyl)dithiooxamide]. The complexes were characterized by elemental analysis as well as by IR, electronic and EPR spectroscopy. These techniques provided evidence for the presence of the CuNO2S chromophore. Magnetic susceptibility measurements on all the complexes in the range 4–300 K show the existence of a dominant antiferromagnetic interaction with −J values greater than 300 cm−1. Therma…

Coordinating properties of the Cephalexine antibiotic. A potentiometric study of the complexes formation between Cephalexine and Co(II), Ni(II) and Cu(II) metal ions

Abstract The formation of complexes between Co(II), Ni(II) and Cu(II) with Cephalexine has been investigated using potentiometric techniques. The stability constants of the complexes formed were calculated using the non-linear least-squares computer program SUPERQUAD. The obtained values were: Co(II) logβ1=2.40, logβMLOH=8.89; Ni(II) logβ1=2.80, logβ2=5.10, logβML2OH=12.09; Cu(II) logβ1=4.094 (25 °C, 0.1 M KNO3). The compound [Ni(CEX)(OH2)4]BPh4 has been synthesized and characterized by electronic, IR and NMR spectroscopies as well as by magnetic measurements. From these studies it is proposed that the Cephalexinate anion acts as a bidentate ligand and is bound to the metal ion through the …

CCDC 1915276: Experimental Crystal Structure Determination

Related Article: Tamara Tŏpala, Alejandro Pascual–Álvarez, M. Ángeles Moldes–Tolosa, Andreea Bodoki, Alfonso Castiñeiras, Javier Torres, Carlos del Pozo, Joaquín Borrás, Gloria Alzuet–Piña|2020|J.Inorg.Biochem.|202|110823|doi:10.1016/j.jinorgbio.2019.110823

CCDC 930871: Experimental Crystal Structure Determination

Related Article: Rubén Gil-García, Roberto Fraile, Bruno Donnadieu, Gotzon Madariaga, Vaidas Januskaitis, Jordi Rovira, Lucía González, Joaquín Borrás, Francisco Javier Arnáiz, Javier García-Tojal|2013|New J.Chem.|37|3568|doi:10.1039/C3NJ00321C

CCDC 1915272: Experimental Crystal Structure Determination

Related Article: Tamara Tŏpala, Alejandro Pascual–Álvarez, M. Ángeles Moldes–Tolosa, Andreea Bodoki, Alfonso Castiñeiras, Javier Torres, Carlos del Pozo, Joaquín Borrás, Gloria Alzuet–Piña|2020|J.Inorg.Biochem.|202|110823|doi:10.1016/j.jinorgbio.2019.110823

CCDC 930872: Experimental Crystal Structure Determination

Related Article: Rubén Gil-García, Roberto Fraile, Bruno Donnadieu, Gotzon Madariaga, Vaidas Januskaitis, Jordi Rovira, Lucía González, Joaquín Borrás, Francisco Javier Arnáiz, Javier García-Tojal|2013|New J.Chem.|37|3568|doi:10.1039/C3NJ00321C

CCDC 1424631: Experimental Crystal Structure Determination

Related Article: Javier García-Tojal, Rubén Gil-García, Víctor Ivo Fouz, Gotzon Madariaga, Luis Lezama, María S. Galletero, Joaquín Borrás, Friederike I. Nollmann, Carlos García-Girón, Raquel Alcaraz, Mónica Cavia-Saiz, Pilar Muñiz, Òscar Palacios, Katia G. Samper, Teófilo Rojo|2018|J.Inorg.Biochem.|180|69|doi:10.1016/j.jinorgbio.2017.12.005

CCDC 1915273: Experimental Crystal Structure Determination

Related Article: Tamara Tŏpala, Alejandro Pascual–Álvarez, M. Ángeles Moldes–Tolosa, Andreea Bodoki, Alfonso Castiñeiras, Javier Torres, Carlos del Pozo, Joaquín Borrás, Gloria Alzuet–Piña|2020|J.Inorg.Biochem.|202|110823|doi:10.1016/j.jinorgbio.2019.110823

CCDC 1919952: Experimental Crystal Structure Determination

Related Article: Tamara Tŏpala, Alejandro Pascual–Álvarez, M. Ángeles Moldes–Tolosa, Andreea Bodoki, Alfonso Castiñeiras, Javier Torres, Carlos del Pozo, Joaquín Borrás, Gloria Alzuet–Piña|2020|J.Inorg.Biochem.|202|110823|doi:10.1016/j.jinorgbio.2019.110823

CCDC 1915275: Experimental Crystal Structure Determination

Related Article: Tamara Tŏpala, Alejandro Pascual–Álvarez, M. Ángeles Moldes–Tolosa, Andreea Bodoki, Alfonso Castiñeiras, Javier Torres, Carlos del Pozo, Joaquín Borrás, Gloria Alzuet–Piña|2020|J.Inorg.Biochem.|202|110823|doi:10.1016/j.jinorgbio.2019.110823

CCDC 1915274: Experimental Crystal Structure Determination

Related Article: Tamara Tŏpala, Alejandro Pascual–Álvarez, M. Ángeles Moldes–Tolosa, Andreea Bodoki, Alfonso Castiñeiras, Javier Torres, Carlos del Pozo, Joaquín Borrás, Gloria Alzuet–Piña|2020|J.Inorg.Biochem.|202|110823|doi:10.1016/j.jinorgbio.2019.110823

CCDC 930874: Experimental Crystal Structure Determination

Related Article: Rubén Gil-García, Roberto Fraile, Bruno Donnadieu, Gotzon Madariaga, Vaidas Januskaitis, Jordi Rovira, Lucía González, Joaquín Borrás, Francisco Javier Arnáiz, Javier García-Tojal|2013|New J.Chem.|37|3568|doi:10.1039/C3NJ00321C

CCDC 930873: Experimental Crystal Structure Determination

Related Article: Rubén Gil-García, Roberto Fraile, Bruno Donnadieu, Gotzon Madariaga, Vaidas Januskaitis, Jordi Rovira, Lucía González, Joaquín Borrás, Francisco Javier Arnáiz, Javier García-Tojal|2013|New J.Chem.|37|3568|doi:10.1039/C3NJ00321C

CCDC 1919951: Experimental Crystal Structure Determination

Related Article: Tamara Tŏpala, Alejandro Pascual–Álvarez, M. Ángeles Moldes–Tolosa, Andreea Bodoki, Alfonso Castiñeiras, Javier Torres, Carlos del Pozo, Joaquín Borrás, Gloria Alzuet–Piña|2020|J.Inorg.Biochem.|202|110823|doi:10.1016/j.jinorgbio.2019.110823

CCDC 930875: Experimental Crystal Structure Determination

Related Article: Rubén Gil-García, Roberto Fraile, Bruno Donnadieu, Gotzon Madariaga, Vaidas Januskaitis, Jordi Rovira, Lucía González, Joaquín Borrás, Francisco Javier Arnáiz, Javier García-Tojal|2013|New J.Chem.|37|3568|doi:10.1039/C3NJ00321C