Antifungal activity of new copper(II) complexes of 2-methylthionicotinate (2-MeSNic) of the composition Cu(2-MeSNic)2(MeNia)(2).4H2O (where MeNia is N-methylnicotinamide), and ...Cu(2-MeSNic)2(Nia)(2).2H2O (where Nia is nicotinamide) and Cu(2-MeSNic)2L2 (where L is isonicotinamide, iNia, or ethyl nicotinate, EtNic) were tested on various strains of filamentous fungi by the macrodilution method. Most sensitive against copper(II) adducts with bioactive ligands were Rhizopus oryzae and Microsporum gypseum (IC50 1.5-2.3 mmol/L). The adducts with Nia, MeNia and EtNic at 5 mmol/L induced morphological changes in growing hyphae of Botrytis cinerea, mainly their intensive branching attached to release of cytoplasm with partial growth inhibition. Inhibition of sporulation (> 90%) of Alternaria alternata by Cu(2-MeSNic)2.H2O was observed as a change in the color of the colonies. The highest resistance was marked by B. cinerea and Fusarium moniliforme (average IC50 values 4.25 and 3.13 mmol/L, respectively). The presence of all bioactive ligands in copper(II) complexes caused an increase in the inhibition effect against model fungi (except significant inhibition activity of EtNic on R. oryzae).
Biological properties of new copper(II) complexes of 2-methylthionicotinate (2-MeSNic) of composition Cu(2-MeSNic)2(MeNia)(2).4H2O (where MeNia is N-methyl-nicotinamide), Cu(2-MeSNic)2(Nia)(2).2H2O ...(where Nia is nicotinamide) and Cu(2-MeSNic)2L2 (where L is isonicotinamide (iNia) or ethyl nicotinate (EtNic)) are reported. Gram(-)-bacteria (Escherichia coli) are more resistant against Cu(II) complexes than Gram(+)-bacteria (Staphylococcus aureus)--significant antistaphylococcal activity was found with Cu(2-MeSNic)2(MeNia)(2).4H2O (IC50 1.3 mmol/L). Candida parapsilosis was most inhibited by Cu(2-MeSNic)2.H2O and Cu(2-MeSNic)2(MeNia)(2).4H2O (IC50 1.4 mmol/L and 1.5 mmol/L, respectively). Biosynthesis of nucleic acids influenced by Cu(2-MeSNic)2(Nia)(2).2H2O indicated by incorporation of 14C-adenine (IC50(Ade) 0.31 mmol/L) is more sensitive than biosynthesis of proteins indicated by incorporation of 14C-leucine (IC50(Leu) 9.94 mmol/L). Cu(II) complexes with expressed antimicrobial activity showed no mutagenic activity.
Reaction of pyrazinecarbonitrile (pz-CN) with copper(II) in methanol solution led to formation of solid complexes containing O-methylpyrazinecarboximidate (pz-C(NH)OMe) as a ligand. The analogous ...reaction of pyrazinecarbonitrile in ethanol led to isolation of solid complexes containing unchanged pz-CN. Six novel copper(II) compounds have been obtained under various reaction conditions. Their stereochemistry and the mode of ligand coordination has been determined by spectroscopic and conductometric measurements. Moreover, the crystal structure of the complex CuCl
2
(O-methylpyrazinecarboximidate)
2
. 2H
2
O has been determined by X-ray diffraction techniques.
Antifungal activity of new copper(II) complexes of 2-methylthionicotinate (2-MeSNic) of the composition Cu(2-MeSNic)2(MeNia)2·4H2O (where MeNia isN-methylnicotinamide), and Cu(2-MeSNic)2(Nia)2·2H2O ...(where Nia is nicotinamide) and Cu(2-MeSNic)2L2 (where L is isonicotinamide, iNia, or ethyl nicotinate, EtNic) were tested on various strains of filamentous fungi by the macrodilution method. Most sensitive against copper(II) adducts with bioactive ligands wereRhizopus oryzae andMicrosporum gypseum (IC50 1.5–2.3 mmol/L). The adducts with Nia, MeNia and EtNic at 5 mmol/L induced morphological changes in growing hyphae ofBotrytis cinerea, mainly their intensive branching attached to release of cytoplasm with partial growth inhibition. Inhibition of sporulation (>90%) ofAlternaria alternata by Cu(2-MeSNic)2·H2O was observed as a change in the color of the colonies. The highest resistance was marked byB. cinerea andFusarium moniliforme (average IC50 values 4.25 and 3.13 mmol/L, respectively). The presence of all bioactive ligands in copper(II) complexes caused an increase in the inhibition effect against model fungi (except significant inhibition activity of EtNic onR. oryzae).
Biological properties of new copper(II) complexes of 2-methylthionicotinate (2-MeSNic) of composition Cu(2-MeSNic)2(MeNia)2·4H2O (where MeNia isN-methylnicotinamide), Cu(2-MeSNic)2(Nia)2·2H2O (where ...Nia is nicotinamide) and Cu(2-MeSNic)2(2 (where L is isonicotinamide (iNia) or ethyl nicotinate (EtNic)) are reported. Gram−-bacteria (Escherichia coli) are more resistant against Cu(II) complexes than Gram+-bacteria (Staphylococcus aureus)—significant antistaphylococcal activity was found with Cu(2-MeSNic)2(MeNia)2·4H2O (IC50 1.3 mmol/L).Caddida parapsilosis was most inhibited by Cu(2-MeSNic)2·H2O and Cu(2-MeSNic)2(MeNia)2·4H2O (IC50 1.4 mmol/L and 1.5 mmol/L, respectively). Biosynthesis of nucleic acids influenced by Cu(2-MeSNic)2-(Nia)2·2H2O indicated by incorporation of14C-adenine (IC50(Ade) 0.31 mmol/L) is more sensitive than biosynthesis of proteins indicated by incorporation of14C-leucine (IC50(Leu) 9.94 mmol/L). Cu(II) complexes with expressed antimicrobial activity showed no mutagenic activity.
The synthesis and characterization of seven new solid complexes, Cu(2-MeSnic)
2(phen) (2-MeSnic
=
2-methylthionicotinate, phen
=
1,10-phenanthroline), CuX
2(bipy)(H
2O) (X
=
2-MeSnic or nic ...(nicotinate), bipy
=
2,2′-bipyridine), Cu(isonic)
2(bipy)(H
2O)
·
H
2O (isonic
=
isonicotinate), Cu(bipy)
2(H
2O)(2-MeSnic)
2
·
3H
2O, Cu(phen)
2(H
2O)(isonic)
2
·
2H
2O and Cu(phen)
2(H
2O)(nic)
2
·
3H
2O, are reported. The composition and stereochemistry as well as the mode of ligand coordination have been determined by elemental analysis, IR, electronic and EPR spectra. In all cases, the available evidence supports square-pyramidal environment about the copper(II) atom, which is confirmed by crystal and molecular structure of one of the products, namely Cu(2-MeSnic)
2(bipy)(H
2O).
The synthesis and characterization of seven new solid complexes, Cu(2-MeSnic)
2 (phen) (2-MeSnic
=
2-methylthionicotinate, phen
=
1,10-phenanthroline), CuX
2(bipy)(H
2O) (X
=
2-MeSnic or nic (nicotinate), bipy
=
2,2′-bipyridine), Cu(isonic)
2(bipy)(H
2O)
·
H
2O (isonic
=
isonicotinate), Cu(bipy)
2(H
2O)(2-MeSnic)
2
·
3H
2O, Cu(phen)
2(H
2O)(isonic)
2
·
2H
2O and Cu(phen)
2(H
2O)(nic)
2
·
3H
2O, are reported. The composition and stereochemistry as well as the mode of ligand coordination have been determined by elemental analysis, IR, electronic and EPR spectra. The carboxyl group of the pyridinecarboxylate anions coordinates to the Cu(II) atom as an unidentate or as a chelating ligand. The EPR spectra of studied complexes are monomeric except for the spectrum of Cu(2-MeSnic)
2(bipy)(H
2O), which shows triplet state feature. Half-field transition, observed for Cu(2-MeSnic)
2(bipy)(H
2O), Cu(bipy)
2(H
2O)(2-MeSnic)
2
·
3H
2O and Cu(phen)
2(H
2O)(nic)
2
·
3H
2O, was used to estimate the interspin copper–copper distances. In all cases, the available evidence supports square-pyramidal environment about the copper(II) atom, which is confirmed by crystal and molecular structure of one of the products, namely Cu(2-MeSnic)
2(bipy)(H
2O). The antimicrobial effects have been tested on various strains of bacteria, yeasts and filamentous fungi.
New copper(II) pyridinecarboxylate compounds of the composition CuX
2(Et
2nia)
2(H
2O)
2 (where X=2-methylthionicotinate (2-MeSnic), 2-chloronicotinate (2-Clnic), 2,6-dichloronicotinate (2,6-Cl
...2nic), isonicotinate (isonic) and Et
2nia=
N,N-diethylnicotinamide) have been prepared. All the CuX
2(Et
2nia)
2(H
2O)
2 compounds seem to possess octahedral copper(II) stereochemistry with differing tetragonal distortions. An X-ray analysis of Cu(2-Clnic)
2(Et
2nia)
2(H
2O)
2 was carried out and it featured a tetragonal-bipyramidal geometry around the copper(II) atom. The tetragonal plane is created by 2-chloronicotinate anions bonded to the copper(II) atom via the unidentate carboxylate oxygen atoms Cu–O1=1.965(2) Å and the pyridine ring nitrogen atoms of the neutral ligand
N,N-diethylnicotinamide Cu–N1=2.015(2) Å, whilst in axial positions are water molecules Cu–O1w=2.503(2) Å.
New copper(II) pyridinecarboxylate compounds of the composition CuX
2(Et
2nia)
2(H
2O)
2 (where X=2-methylthionicotinate (2-MeSnic), 2-chloro-nicotinate (2-Clnic), 2,6-dichloronicotinate (2,6-Cl
2nic), isonicotinate (isonic) and Et
2nia=
N,
N-diethylnicotinamide) have been prepared. All the CuX
2(Et
2nia)
2(H
2O)
2 compounds seem to possess octahedral copper(II) stereochemistry with differing tetragonal distortions. An X-ray analysis of Cu(2-Clnic)
2(Et
2nia)
2(H
2O)
2 was carried out and it featured a tetragonal-bipyramidal geometry around the copper(II) atom.
The synthesis and characterization of Cu
2(2-MeSnic)
4(H
2O)
2, Cu(2-MeSnic)
2(en), Cu(en)
2(H
2O)
2(2-MeSnic)
2 and Cu(dien)(H
2O)
2(2-MeSnic)
2 (where 2-MeSnic=2-methylthionicotinate, ...en=ethylenediamine, dien=diethylenetriamine) is reported. The characterizations were based on elemental analysis, infrared, electronic and EPR spectra, and magnetic susceptibility measurements over a temperature range of 1.9–300 K. The available evidence supports a dimeric structure for Cu
2(2-MeSnic)
4(H
2O)
2 and for Cu(en)
2(H
2O)
2(2-MeSnic)
2 a tetragonal-bipyramidal environment about the copper(II) atom. The other two complexes were studied also by X-ray analysis. The Cu(dien)(H
2O)
2(2-MeSnic)
2 crystallizes in the monoclinic system. The copper(II) atom has a square-pyramidal arrangement, with three nitrogen atoms of the tridentate diethylenetriamine and one water molecule in the base of the pyramid, and the remaining water molecule occupies the apical position. The copper(II) atom deviates from the basal plane by 0.1164(5) Å toward the water molecule in the apical position. The copper(II) atom in Cu(2-MeSnic)
2(en) is coordinated by two symmetry-dependent nitrogen atoms of ethylenediamine and by two pairs of non-equivalently coordinated carboxyl oxygen atoms of two symmetry-dependent 2-methylthionicotinates with CuO bond distances of 1.975(2) and 2.564(2) Å, respectively, resulting in a highly distorted tetragonal-bipyramidal coordination.
Synthesis and characterization of seven new complexes Cu(2‐MeSnic)2(CH3OH)2 (where 2‐MeSnic is 2‐methylthionicotinate), Cu(2‐MeSnic)2L22 (where L is pyridine — py, ethylnicotinate — Etnic and ...butylnicotinate — Bunic), Cu(2‐MeSnic)2L2(H2O)2 (where L is py and nicotinamide — nia) and Cu(2‐MeSnic)2(N‐Menia)2(H2O)2·2H2O (where N‐Menia is N‐methylnicotinamide) are reported. The characterization were based on elemental analysis, infrared, electronic and EPR spectra, and magnetic susceptibility measurements over a temperature range of 1.8 — 300 K or 70 — 300 K. Three complexes of different type were studied by X‐ray analysis. The molecule of Cu(2‐MeSnic)2(CH3OH)2 has dimeric paddle‐wheel cage structure with a tetragonal pyramidal arrangement around CuII. The dimer results from the fact that carboxyl groups of four 2‐MeSnic anions function as bridging in a syn‐syn arrangement. On the other hand Cu(2‐MeSnic)2(py)22 forms dimers with hexacoordinated CuII atoms in highly distorted coordination octahedra, each with two oxygen atoms of bridging carboxyl groups in an anti‐anti arrangement of two 2‐MeSnic anions, with two oxygen atoms of one asymmetrically chelating 2‐MeSnic anion and with two nitrogen atoms of two pyridine ligands. The temperature independent EPR spectrum for this complex exhibits an axial signal which corresponds to almost isolated S = 1/2 magnetic ions. Magnetic data for the dimer show a weak antiferromagnetic interaction between the two metal ions with J = —0.65 cm—1. The CuII atom in complex Cu(2‐MeSnic)2(py)2(H2O)2 is hexacoordinated in an elongated centrosymmetrical tetragonal‐bipyramidal arrangement (4 + 2). Based on the molecular structure the electronic, infrared, electron paramagnetic resonance spectra and magnetic properties are discussed and stereochemistry as well as the mode of ligand coordination in new solid complexes under study have been determined.
Synthese, spektroskopische und magnetische Eigenschaften und Kristallstrukturen von Kupfer(II)‐pyridincarboxylato‐Addukten mit N‐heterozyklischen Liganden
Die Synthese und Charakterisierung von sieben neuen Komplexen: Cu(2‐MeSnic)2(CH3OH)2 (2‐MeSnic: 2‐Methylthionicotinat), Cu(2‐MeSnic)2L22 (L: Pyridin — py, Ethylnicotinat — Etnic und Butylnicotinat — Bunic), Cu(2‐MeSnic)2L2(H2O)2 (L: py und Nicotinamid — nia) und Cu(2‐MeSnic)2(N‐Menia)2(H2O)2·2H2O (N‐Menia: N‐Methylnicotinamid) wird mitgeteilt. Die Charakterisierungen erfolgen durch Elementaranalysen, Infrarot‐, elektronischer und EPR‐Spektroskopie sowie Messung der magnetischen Suszeptibilität über einen Temperaturbereich von 1, 8—300 K bzw. 70—300 K. Drei unterschiedliche Komplextypen wurden mit Hilfe der Röntgenstrukturanalyse gefunden. Das Molekül Cu(2‐MeSnic)2(CH3OH)2 hat eine Schaufelrad‐Käfigstruktur mit CuII in einer tetragonal‐pyramidalen Umgebung. Das Dimer resultiert aus der Tatsache, dass die Carboxylgruppen der vier 2‐MeSnic‐Anionen verbrückend in einer syn‐syn‐Anordnung fungieren. Cu(2‐MeSnic)2(py)22 hingegen bildet Dimere mit sechsfach koordinierten CuII Ionen in einem stark verzerrten Koordinationsoktaeder, jeweils verbunden mit zwei Sauerstoff Atomen der verbrückenden Carboxylgruppen in einer anti‐anti‐Anordnung der beiden 2‐MeSnic‐Anionen, mit zwei Sauerstoff‐Atomen eines asymmetrisch chelatisierenden 2‐MeSnic‐Anions und den Stickstoff‐Atomen der beiden Pyridin‐Liganden. Das temperaturunabhängige EPR‐Spektrum dieses Komplexes liefert ein axiales Signal in Übereinstimmung mit nahezu isolierten magnetischen S = 1/2 Ionen. Die magnetischen Daten des Dimer belegen eine schwache antiferromagnetische Wechselwirkung zwischen den beiden Metallionen mit J = ‐0.65 cm—1. Das CuII‐Atom des Komplexes Cu(2‐MeSnic)2(py)2(H2O)2 ist sechsfach koordiniert in einer gestreckten zentrosymmetrisch tetragonal‐bipyramidalen Umgebung (4 + 2). Ausgehend von der molekularen Struktur werden die elektronischen, infraroten, EPR und magnetischen Eigenschaften diskutiert und sowohl die Stereochemie als auch das Koordinationsverhalten der neuen Verbindungen beschrieben.
The reaction of an ethanolic solution of copper(II) pyridinecarboxylates CuX
2·
nH
2O (where X is nicotinate (nic) (
n=0) or isonicotinate (isonic) (
n=4)) with ethylenediamine (en) in a molar ratio ...of 1:2 lead to the isolation of solid tetragonally distorted octahedral complexes of the type Cu(en)
2(H
2O)
2X
2·
nH
2O (
n=1 for nic;
n=0 for isonic). The analogous reaction of CuX
2·
nH
2O with diethylenetriamine (dien) in a molar ratio of 1:1 leads to the formation of square-pyramidal pentacoordinated complexes of the type CuX(dien)(H
2O)X. On the other hand, the reaction of equimolar quantities of copper(II) nitrate and dien with nicotinate anions (equimolar quantities of pyridinecarboxylic acid and NaOH) in ethanolic solutions gives a solid monomeric complex Cu(nic)(NO
3)dien)(H
2O)·H
2O in which the coordination polyhedron around the Cu(II) atom is a (4+1+1) distorted tetragonal bipyramid. Based on the molecular structure the electronic and IR spectra are discussed. Moreover, the results of the quantitative determination of antimicrobial activity of the isonic complexes Cu(isonic)
2(H
2O)
4, Cu(en)
2(H
2O)
2(isonic)
2, Cu(isonic)(dien)(H
2O)(isonic), as well as isonicotinic acid, ethylenediamine and diethylenetriamine alone are discussed.
