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…

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…

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.

Structural basis and effect of copper(II) complexes with 4-oxo-thiazolidine ligands on DNA binding and nuclease activity

Abstract Seven novel Copper(II) complexes, namely [Cu(Am4DHotaz)(H2O)2](ClO4) (1), [Cu(Am4DHotaz)(NO3)(MeOH)]·H2O (2), [Cu(Am4Motaz)2(H2O)](ClO4)2·0.83H2O (3), [Cu(Am4Motaz)2(NO3)]NO3·MeOH (4), [Cu(Am4Eotaz)2(NO3)]3(NO3)3·2H2O (5), [Cu(Am4Eotaz)2(ClO4)](ClO4) (6) and [Cu(Am4Eotaz)(ClO4)(H2O)](ClO4) (6a) (HAm4DHotaz = N′-(4-oxothiazolidin-2-ylidene)pyridine-2-carbohydrazonamide, Am4Motaz = N′-(3-methyl-4-oxothiazolidin-2-ylidene)pyridine-2-carbohydrazonamide and Am4Eotaz = N′-(3-ethyl-4-oxothiazolidin-2-ylidene)pyridine-2-carbohydrazonamide), have been successfully synthesized and characterized by several physicochemical techniques and, for 1–6 complexes, single crystal X-ray diffraction. Ha…

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…

Two copper complexes from two novel naphthalene-sulfonyl-triazole ligands: different nuclearity and different DNA binding and cleavage capabilities.

[EN] Two novel naphthalene-sulfonyl-triazole ligands, 5-amino-N1-(naphthalen-3-ylsulfony1)-1,2,4-triazole (anstrz) and 3,5-diamino-N1-(naphthalen-3-ylsulfony1)-1,2,4-triazole (danstrz), purposely designed to interact with DNA, have been prepared for the first time and then fully characterized by H-1, C-13 NMR and IR spectroscopy, mass spectrometry and elemental analysis. The crystal structures of two copper complexes of these derivatives, i.e. [Cu(anstrz)(4)(NO3)(2)]center dot 4CH(3)OH (1), mononuclear, and [Cu(danstrz)(mu-OAc)(2)](2)center dot 2(danstrz) (OAc = acetato) (2), dinuclear, have been determined by single-crystal X-ray diffraction. In both cases the ligand coordinates in a monod…

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…

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…

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…

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 …

Ni(II) and Zn(II) complexes with cinoxacin. Synthesis and characterization of M(Cx)2(DMSO)n(H2O)m (n=0, 2; m=2, 4). Crystal structures of [M(Cx)2(DMSO)2]·4H2O (M=Ni(II), Zn(II))

Abstract New metal complexes of cinoxacin (HCx=1-ethyl-l,4-dihydro-4-oxo(1,3)dioxolo(4,5-g)cinnoline-3-carboxylic acid) were synthesized, isolated as [Zn(Cx)2(DMSO)2]·4H2O, [Ni(Cx)2(DMSO)2]·4H2O, Zn(Cx)2·4H20 and Ni(Cx)2·2H2O, and characterized by elemental analysis, TG studies, IR and UVVis spectroscopic techniques. The crystal and molecular structures of the complexes [M(Cx)2(DMSO)2]·4H2O (M=Zn(II), Ni(II)) have been determined by X-ray structure analysis. The crystals of [Zn(Cx)2(DMSO)2]·4H2O are triclinic, space group P 1 with unit cell dimensions a=8.950(4), b=9.168(5), c=11.650(6) A, α=69.06(1), β=82.05(1), γ=75.63(1)°, V=863.6(8) A3; [Ni(Cx)2(DMSO)2]·4H20 is monoclinic, space group …

Hexanuclear Cu3O–3Cu triazole-based units as novel core motifs for high nuclearity copper(ii) frameworks

The asymmetric 3,5-disubstituted 1,2,4-triazole ligand H2V (5-amino-3-picolinamido-1,2,4-triazole) by reaction with an excess of Cu(II) perchlorate (Cu : H2V being 12 : 1) has produced a novel hexanuclear {Cu6(m3-O/H)(HV/V)3} fragment, with one triangular Cu3(m3-O/H) group connected to three peripheral single Cu(II) ions through a cis–cis–trans bridging mode of the ligand, which is the building block of the three structures described here: one hexanuclear, [Cu6(m3-O)(HV)3(ClO4)7(H2O)9]$8H2O (1), one dodecanuclear, [Cu12(m3-O)2(V)6(ClO4)5(H2O)18](ClO4)3$6H2O (2), and one tetradecanuclear 1D-polymer, {[Cu14(m3-OH)2(V)6(HV)(ClO4)11(H2O)20](ClO4)2$14H2O}n (3), the last two containing hexanuclea…

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…

Two Novel Ternary Dicopper(II) μ-Guanazole Complexes with Aromatic Amines Strongly Activated by Quantum Dots for DNA Cleavage

Two novel (μ-guanazole)-bridged binuclear copper(II) complexes with 1,10-phenanthroline (phen) or 2,2'-bipyridine (bipy), [Cu2(μ-N2,N4-Hdatrz)(phen)2(H2O)(NO3)4] (1) and [Cu2(μ-N1,N2-datrz)2(μ-OH2)(bipy)2](ClO4)2 (2) (Hdatrz = 3,5-diamino-1,2,4-triazole = guanazole), have been prepared and characterized by X-ray diffraction, spectroscopy, and susceptibility measurements. Compounds 1 and 2 differ in the aromatic amine, which acts as a coligand, and in the Cu···Cu'-bridging system. Compound 1, which contains two mono-bridged copper ions, represents the first example of a discrete Cu-(NCN-trz)-Cu' complex. Compound 2, with two triply bridged copper ions, is one of the few compounds featuring a…

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

Novel Hexanuclear Copper(II) Complex Built from a Simple Tetrachelating Triazole Ligand: Synthesis, Structure, and Magnetism

A new easy symmetric 3,5-disubstituted 1,2,4-triazole ligand (H3diV) by reaction with an excess of copper(II) salt has afforded a novel hexanuclear compound (Cu/HdiV ratio of 6:2) through a bis(trans-cis-cis-trans) binding mode, exhibiting two types of Cu(II) centers and two clearly distinguishable antiferromagnetic J1 (-234 cm(-1)) and J2 (-35 cm(-1)) coupling constants.

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…

Interactions of metal ions with a 2,4-diaminopyrimidine derivative (trimethoprim)

The interaction of copper (II), zinc(II) and cadmium(II) with Trimethoprim (2,4-diamino-5-(3',4',5'-trimethoxybenzyl) pyrimidine) has been studied. The crystal structures of [Zn(Trim)2Cl2] (2) and [Cd(Trim)Cl2(CH3OH)]n (4) are reported. Compound (2) exhibits a distorted tetrahedral environment around the metal center and crystallizes in the triclinic space group P1 with a=10.2397(6), b=10.4500(6), c=16.3336(16) A, alpha=96.141(8), beta=106.085(5), gamma=96.551(5) degrees and Z=2. In complex (4), the Cd(II) centers are bridged sequentially by two chlorine ions to form infinite chains and present a six-coordinated environment; the compound crystallizes in the monoclinic P2(1)/C space group wi…

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…

Synthesis, characterization, and crystal structure of [Cu(cinoxacinate)2] · 2H2O complex: A square-planar CuO4 chromophore. Antibacterial studies

The structural and spectroscopic properties of a new copper (II) complex of cinoxacin (HCx) have been investigated. The complex [Cu(Cx)2].2H2O crystallizes in the monoclinic system, space group P2(1)/c. The cell dimensions are: a = 7.998(2), b = 7.622(1), c = 18.955(6) A, beta = 94.38(2) degree, V = 1154.6(6) A3, Z = 2. The structure was refined to R = 0.051. The crystal is composed of [Cu(Cx)2] units and uncoordinated water molecules. The Cu(II) ion, at a center of symmetry, is coordinated to two cinoxacinate (Cx) ligands related by the inversion center. Each cinoxacinate acts as bidentate ligand bonded to the cation through its carboxylate oxygen atom and through its exocyclic carbonyl ox…

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...

N-(5-Amino-1H-1,2,4-triazol-3-yl)pyridine-2-carboxamide

The title compound, C8H8N6O, was obtained by the reaction of 3,5-diamino-1,2,4-triazole with ethyl 2-picolinate in a glass oven. The dihedral angles formed between the plane of the amide group and the pyridine and triazole rings are 11.8 (3) and 5.8 (3)°, respectively. In the crystal, an extensive system of classical N—H...N and N—H...O hydrogen bonds generate an infinite three-dimensional network.

A Unique Discrete Tetranuclear Cu′–Cu(N-N)2Cu–Cu′ Copper(II) Complex, Built from a μ3-1,2,4-Triazolato-μ-carboxylato Ligand, as an Effective DNA Cleavage Agent

The title compound, characterized by means of an X-ray structure analysis, represents an easy example of a noncatena "1 + 2 + 1" tetranuclear copper(II) μ(3)-triazolate compound. [Cu(4)(atc)(2)(dien)(4)(ClO(4))(2)](ClO(4))(2)·2H(2)O (1), where H(2)atc = 5-amino-l,2,4-triazole-3-carboxylic acid and dien = diethylenetriamine = 1,4,7-triazaheptane, contains two copper atoms linked by a double diazinic bridge, each of which is further connected to a third and fourth copper atom (Cu') through the triply bridging triazolato ring and the bidentate carboxylato group of the atc(2-) ligands. The copper-copper distances within the tetranuclear unit are Cu-Cu = 4.059 Å, Cu-Cu' = 5.686 and 6.370 Å, and …

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…

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…

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…

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…

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.

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.

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…

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…

CCDC 1941350: Experimental Crystal Structure Determination

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CCDC 1915276: Experimental Crystal Structure Determination

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CCDC 1915272: Experimental Crystal Structure Determination

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CCDC 907781: Experimental Crystal Structure Determination

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CCDC 1941349: Experimental Crystal Structure Determination

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CCDC 1935980: Experimental Crystal Structure Determination

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CCDC 1919951: Experimental Crystal Structure Determination

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CCDC 1941353: Experimental Crystal Structure Determination

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