Browsing by Author "Țapcov, Victor"

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COBALT, NICKEL, AND COPPER COORDINATION COMPOUNDS WITH 3-PHENYLPROPENAL BENZOYLHYDRAZONE
(2006) Samusi, Nina; Gulea, Aurelian; Țapcov, Victor
3-Phenylpropenal benzoylhydrazone (HL) reacts with cobalt, nickel, and copper chlorides, nitrates, and acetates to give coordination compounds MX 2 • nH2O [M = Co, Ni, Cu; X = Cl, NO3, HL = C6H5CH=CHCH=NNHC(O)C6H5; n = 0, 2] and ML2 • nH2O (M = Co, Ni, Cu; n = 1-3). Complexes MALCI (M = Co, Ni, Cu) were obtained by these reactions in the presence of amines (A = C5H5N, 2-CH3C5H 4N, 3-CH3C5H4N, 4-CH 3C5H4N). All the compounds have a monomeric structure. Azomethine (HL) in them behaves as a bidentate N,O-ligand. Thermolysis of the complexes involves the stages of dehydration (70-90°C), deaquation (145-155°C) or deamination (145-185°C), and complete thermal decomposition (330-490°C).
COORDINATION COMPOUND AS INHIBITOR OF SUPEROXID RADICAL
(2019) Garbuz, Olga; Pantea, Valeria; Usataia, Irina; Graur, Vasilii; Țapcov, Victor; Sardari, Veronica; Tagadiuc, Olga; Gudumac, Valentin; Gulea, Aurelian
A fost obținut un nou compus coordinativ biologic activ, nitratul de cupru [2 - ({2 [(ethylsulfanyl) (prop-2-en-1-yl) carbononoimidooyl] -hydrazinylidene} methyl) phenolate], care face parte din clasa isotiosemicarbazidelor metalelor de tranziție.S-a stabilit că acesta exercită proprietăți anti radicalice performante la acțiunea moleculei organice cu radicalul superoxidic. Datorită acestei poroprietăți compusul obținut poate avea o potențială aplicare in medicină in calitate de inhibitor al radicalilor superoxidici in corpul uman, care poate duce la prevenirea deteriorării tesutului cellular, aterosclerozii si carcinogenezei.Compusul coordinativ sintetizat extinde arsenalul inhibitorilor de radicali superoxidici cu activitate biologică importanta.
COORDINATION COMPOUNDS OF COBALT, NICKEL, AND COPPER WITH ISONITROSOACETONE BENZOYLHYDRAZONE
(2002) Țapcov, Victor
Benzoylhydrazine and isonitrosoacetone react in ethanol with cobalt, nickel, and copper halides and acetates to give the coordination compounds MX2(HL)·nH2O, MX2(HL) 2·nH2O, and ML2·nH2O [M = Co, Ni, Cu; X = Cl, Br; HL = C6H5C(O)NHNC(CH 3)CHNOH; n = 1-4]. The same reactions performed in the presence of sodium acetate and pyridine (pH 7-8) yield the complexes MLCl·nH 2O and MPy2LCl·nH2O (n = 1-4). All the complexes have a pseudooctahedral coordination geometry. The hydrazone HL behaves as a tridentate O,N,N-donor ligand. Thermolysis of the substances involves dehydration (70-90°C), deaquation (155-170°C) or deamination (175-195°C), and complete thermal decomposition (285-360°C).
COORDINATION COMPOUNDS OF COBALT, NICKEL, COPPER AND ZINC WITH THIOSEMICARBAZONE AND 3-PHENYLPROPENAL SEMICARBAZONE
(2006) Samusi, Nina; Gulea, Aurelian; Țapcov, Victor; Ciumacov, Iurie; Roșu, Tudor
Hydrates of 3-phenylpropenal thiosemicarbazone (HL•H2O) and semicarbazone (HL'•H2O) react in methanol with cobalt, nickel, copper, and zinc chlorides, nitrates, and acetates to form coordination compounds MX2•2HL•nSolv [M = Co, Ni, Cu, Zn; X = Cl, NO3; HL = C6H5CH=CH-CH=N-NHC(O)NH2; n = 0-3; Solv = H2O, CH3OH], CuX2•HL• nH2O [M = Ni, Cu; n = 0, 1], ML2•nH2O and ML'•nH2O [M = Co, Ni, Zn; HL' = C6H 5CH=CH-CH=N-NHC(O)NH2; n = 0-3]. In the presence of amines (A = C5H5N, 2-CH3C5H4N, 3-CH3C5H4N, and 4-CH3C 5H4N) these reactions yield the complexes Cu(A)LCl•CH3OH and M(A)LX•nH2O [M = Cu, Ni; X = Cl, NO3; n = 0-2]. The copper complexes with the amine ligands are of polynuclear structure, and other complexes are monomeric. Carbazones (HL and HL') are included in the complexes as bidentate N,S-and N,O-ligands. The thermolysis of the complexes involves the stages of removing solvent crystallization molecules (70-90°C), deaquation (150-170°C), and full thermal decomposition (500-580°C).
COORDINATION COMPOUNDS OF COBALT, NICKEL, COPPER, AND ZINC WITH 2-BROMO-3-PHENYLPROPENAL BENZOYLHYDRAZONE AND THIOSEMICARBAZONE
(2009) Samusi, Nina; Ciumacov, Iurie; Țapcov, Victor; Bocelli, Gabrielle; Simonov, Iurie; Gulea, Aurelian
By X-ray structural analysis the crystal structure of 2-bromo-3- phenylpropenal benzoylhydrazone (HL) was determined. The molecule is not flat. In the crystal the HL molecules form infinite chains with reciprocal van der Waals interaction. 2-Bromo-3-phenylpropenal hydrazone (HL) and thiosemicarbazone (HL') react with cobalt, nickel, copper and zinc chlorides, nitrates and acetates to form coordination compounds of the composition Cu(HL)(L)2 [HL = C6H5-CH=CBr-CH=N-NH-C(O)-C6H 5], MX2•2 HL'•nH2O [M = Co, Ni, Cu, Zn; X = Cl, NO3, HL' = C6H5-CH=CBr-CH=N-NH-C(S) -NH2; n = 0-3], MX2•HL•n H2O [M = Ni, Cu; n = 0, 1], and ML'2•nH2O [M = Co, Ni, Zn; n = 0-3]. The same reactions in the presence of amines (A = C5H 5N, 2-CH3C5H4N, 3-CH 3C5H4N, 4-CH3C5H 4N) afford complexes of the composition CuALCl and MALX•n H 2O [M = Cu, Ni; X = Cl, NO3; n = 0-2]. Structure of the coordination node in the amine-containing copper derivatives is polynuclear, in complexes Cu(HL)(L)2 is octahedral, in other compounds it is tetrahedral. The azomethines (HL and HL') in these complexes behave as bidentate N,O and N,S ligands. Thermolysis of the complexes includes a step of dehydration (60-90°C) and complete thermal decomposition (430-590°C).
COORDINATION COMPOUNDS OF COBALT, NICKEL, COPPER, AND ZINC WITH N1,N2 -BIS(PYRIDIN-2-YLMETHYLIDENE)BENZENE-1,2-DIAMINE AND ITS DERIVATIVES
(2014) Pahonțu, Elena; Gulea, Aurelian; Poirier, Donald; Țapcov, Victor
o-Phenylenediamine reacts with 2-formyl-, 2-acetyl-, or 2-benzoylpyridine in ethanol in the presence of cobalt, nickel, copper, or zinc chlorides to form monomeric complexes ML1-3Cl2·nH2O {M = Co, Ni, Cu, Zn; L1 = N 1,N 2-bis(pyridin-2-ymethylidene)benzene-1,2-diamine, L2 = N 1,N 2-bis(pyridin-2-ylethylidene) benzene-1,2-diamine, L3 = N 1,N 2-bis[phenyl(pyridin-2-yl)methylidene]benzene-1,2-diamine; n = 0-3}. The condensation products (L1-L3) act in the complexes as tetradentate N,N,N,N-ligands. Thermolysis of the complexes occurs in two stages: dehydration (70-95°C) and complete degradation (320-450°C). At concentrations of 10-5-10-7 M, the complexes inhibit in vitro growth and proliferation of HL-60 human promyelocytic leukemia cells.
COORDINATION COMPOUNDS OF COPPER AND NICKEL WITH N,N'-[4,4'-(PERFLUORO-1,4-PHENYLENE)BIS(OXY)BIS(4,1-PHENYLENE)]- BIS[2-(PYRIDIN-2-YLMETHYLIDENE)HYDRAZINECARBOTHIOAMIDE] AND ITS DERIVATIVES
(2014) Pahonțu, Elena; Țapcov, Victor; Poirier, Donald; Gulea, Aurelian
N,N′-[4,4′-(Perfluoro-1,4-phenylene)bis(oxy)bis(4,1-phenylene)] bis[2-(pyridin-2-ylmethylidene)-hydrazinecarbothioamide] as well as its methyl and phenyl derivatives react with copper and nickel chlorides in ethanol to form coordination compounds. In the products, the hydrazinecarbothioamides act as doubly deprotonated bridging ligands. The prepared complexes have been found to inhibit in vitro the growth and propagation of the myeloid human leukemia HL-60 cancer cells at the 10-5-10-7 mol/L concentration.
COORDINATION COMPOUNDS OF COPPER WITH 2-FORMYLPYRIDINE 4-(DIMETHYLPHENYL)THIOSEMICARBAZONES
(2012) Gulea, Aurelian; Lozan-Tîrșu, Carolina; Țapcov, Victor; Corja, Ion; Rudic, Valeriu
2-Formylpyridine 4-(2,6-dimethylphenyl)-(HL1), 4-(2,5-dimethylphenyl)-(HL2), 4-(3,4-dimethylphenyl)-(HL 3), and 4-(2,4-dimethylphenyl)thiosemicarbazones (HL4) react with copper chloride and nitrate to form coordination compounds CuL 1-4X·nH2O [X = Cl-, NO3 -; n = 1, 2]. All compounds have a polynuclear structure. Azomethines HL1-4 act as the bridging monodeprotonated tridentate N,N,S-ligands. The thermolysis of the complexes includes the dehydration (70-90 C) and total thermal decomposition (350-520 C). The complexes synthesized exhibit a selective antimicrobial activity against a series of standard strains of Staphylococcus aureus and Escherichia coli in the concentration range of 0.009-37.5 μg ml-1
COORDINATION COMPOUNDS OF COPPER(II) NITRATE WITH PRODUCTS OF AMINOTRIS(HYDROXYMETHYL)METHANE CONDENSATION WITH SALICYL- AND 5-NITROSALICYLALDEHYDES: SYNTHESIS AND CRYSTAL STRUCTURES
(2005) Ciumacov, Iurie; Țapcov, Victor; Simonov, Iurie; Antoșciac, Boris; Bocelli, Gabrielle; Perrin, Monique; Starnicova, Zoia; Samusi, Nina; Gulea, Aurelian
The crystal structures of copper(II) nitrate complexes with 2-(2-hydroxybenzylideneamino)-2-hydroxymethylpropane-1,3-diol (HL) and 2-hydroxymethyl-2-(2-hydroxy-5-nitrobenzylideneamino)propane-1,3-diol (HL 1) were determined. The resulting complexes were formulated as [Cu3OL3(H2O2]NO3 • 3H2O (I) and [Cu(H2O)L1]NO3 (II). The crystals of I are monoclinic, a = 17.809(4) Å, b = 30.549(6) Å, c = 18.962(4) Å, β = 115.36(3)°, space group Cc, Z = 8, R = 0.0482. Complex I is composed of two independent three-dimensional μ 3-oxo complexes; the coordination polyhedron of the copper atoms in both compounds is an elongated tetragonal bipyramid. The coordination polyhedron of the third Cu atom is a tetragonal pyramid. The bases of the pyramids are composed of the oxygen atoms of the phenol and alcohol OH groups, the imine N atom of ligand L, and μ 3-oxo atoms. The phenol and water O atoms serve as the apices in both the tetragonal bipyramids. The crystals of II are triclinic, a = 6.062(1) Å, b = 7.701(2) Å, c = 16.162(3) ̊, α = 88.15(3)°, β = 84.94(3)°, γ = 78.13(3)°, space group P1̄, Z = 2, R = 0.0272. Complex II is composed of polymer chains formed by coordination bonds between the copper atom and two O atoms of the amino alcohol in the azomethine of the neighboring complex connected to the initial one by translation along the x axis. These chains are linked through hydrogen bonds involving the oxygen atoms of the NO2 groups. The benzene rings of the azomethine ligands of the adjoining complexes from different chains are antiparallel to each other. The coordination polyhedron of the central atom is an elongated tetragonal bipyramid. Its equatorial plane is formed by the phenol O atom, one of the alcohol O atoms, the N atom of ligand L1, and the O atom of the amino alcohol in the neighboring complex. The apices are the O atom of the water molecule and the O atom of the amino alcohol in the neighboring azomethine molecule. In complexes I and II, the outer-sphere nitrato group mainly serves to unite trimers and polymers in the crystal by means of hydrogen bonds.
COORDINATION COMPOUNDS OF COPPER(II) WITH BENZOYLHYDRAZONES OF SUBSTITUTED SALICYLALDEHYDES
(2003) Samusi, Nina; Țapcov, Victor; Kerner, A.
Benzoylhydrazones of 5-nitro- (H2L1), 3-nitro- (H2L2), 5-chloro- (H2L3), 5-bromo- (H2L4), and 3,5-dibromosalicylaldehydes (H 2L5) react in ethanol with copper acetate to form complexes CuL1-5. In the presence of amines (A = C5H 5N, 3-CH3C5H4N), the above reactions give complexes CuL1-5A·nH2O (n = 0, 1). When cuprous bromide or nitrate and benzoylhydrazone H2L3 were used as starting materials, complexes Cu(HL3)X (X = Br-, NO3-) were isolated. The resulting complexes all are polynuclear structures in which azomethines H2L1-5 behave as tridentate O,N,O-ligands. Thermolysis of the complexes involves the stages of dehydration (70-90°C), deaquation (120-150°C) or deamination (150-180°C), and complete thermal decomposition (350-500°C).
COORDINATION COMPOUNDS OF COPPER(II) WITH SUBSTITUTED 3-{[(2-HYDROXYPHENYL)METHYLIDENE]AMINO}PROPANE-1,2-DIOLS
(2013) Gulea, Aurelian; Ciumacov, Iurie; Graur, Vasilii; Țapcov, Victor
3-{[(2-Hydroxyphenyl)methylidene]amino}propane-1,2-diol, its 5-chloro-,5-bromo-, 5-nitro-, 3-methoxy derivatives, and 3-{[(2-hydroxynaphthyl- 1)methylidene]amino}propane-1,2-diol react with hydrates of copper(II) chloride, bromide and nitrate in ethanol to form coordination compounds Cu(L)X·nH2O. Template condensation reaction between 3-aminopropane-1,2-diol and 2,3-, 2,4- or 2,5-dihydroxybenzaldehyde in the presence of copper(II) nitrate trihydrate results in similar compounds Cu(L)NO3·nH2O. Structure of some of the condensation products was identified by X-ray analysis. Thermolysis of the substances obtained occurs through the dehydration step (70-90 C) and complete thermal decomposition (290-560 C).
COORDINATION COMPOUNDS OF COPPER(II), NICKEL(II), AND COBALT(II) WITH β-THIOSEMICARBAZONES OF ISATIN AND N-METHYLISATIN
(2004) Samusi, Nina; Țapcov, Victor; Gulea, Aurelian
Isatin thiosemicarbazone (HL) reacts in aquoeus-ethanolic medium with copper(II) chloride and bromide (pH 7-7.5, ethanolic KOH) to give coordination compounds CuLX·nH2O (X = Cl, Br; n = 3, 4). In the presence of amines (A = C5H5N, 3-CH3C5H 4N, and 4-CH3C5H4N), complexes CuALX·2H2O and CuA2LX·H2O (X = Cl, Br) are formed. With nickel(II) or cobalt(II) chlorides, thiosemicarbazone HL, and pyridine (1:1:3) as starting compounds, compounds MPy 2LCl·H2O (M = Ni, Co) are isolated. Under similar conditions, N-methylisatin β-thiosemicarbazone (HL') reacts with chlorides of the above-noted metals in the presence of pyridine to give complexes MPy 2L'Cl·H2O (M = Cu, Ni, Co). All the complexes are monomeric and have a pseudooctahedral structure of the coordination unit. Thiosemicarbazones HL and HL1 in these complexes behave as tridentate monodeprotonated O,N,S-ligands. Thermolysis of these substances passes through the stages of dehydration (60-90°C), deaquation (135-140°C) or deamination (160-215°C), and complete thermal decomposition (560-670°C).
CRYSTAL STRUCTURE OF 4,4-BIPYRIDINE-CONTAINING COMPLEXES OF COPPER(II) NITRATE WITH 1-[(2-HYDROXYETHYLIMINO)METHYL]NAPHTHALEN-2-OL AND 2-[(2-HYDROXYETHYLIMINO)METHYL]PHENOL
(2009) Ciumacov, Iurie; Țapcov, Victor; Petrenko, Peter A.; Popovschi, Liliana; Simonov, Iurie; Bocelli, Gabrielle; Antoșciac, Boris; Paraschivescu, Andrei; Gulea, Aurelian
The crystal structures of (μ-4,4-bipyridine)-di(nitrato-1-[(2- hydroxyethylimino)methyl]naphthalen-2-olocopper (I) and catena-di(μ-4,4'- bipyridine)di(μ-4,4'-bipyridine)-di(nitrato-2-[2-(hydroxyethylimino) methyl]phenolocopper)diaquacopper(II) nitrate (II) were determined. In the crystal of I, each of the two copper atoms coordinates a singly deprotonated tridentate azomethine molecule, a nitrate ion, and bipyridine, which functions as a bridge between the central atoms. The copper coordination polyhedron is a slightly distorted tetragonal pyramid with the base formed by the imine and bipyridine nitrogen atoms and the phenol and alcohol oxygen atoms. The axial site in the pyramid is occupied by the oxygen atom of the monodentate nitrate groups. In the trinuclear structure II with C2 crystal chemical symmetry, the terminal coordination unit is composed through copper coordination of monodeprotonated 2-[2-(hydroxyethylimino)methyl]phenol, bipyridine, and the nitrate anion. In the crystal, the trinuclear molecules form infinite ribbons along the z axis in which the pyridine molecules perform the bridging function. The central copper atom has an octahedral configuration formed by the nitrogen atoms of four 4,4'-bipyridine molecules and oxygen of two water molecules
CRYSTAL STRUCTURE OF COPPER SULFATE AND THIOCYANATE COMPLEXES WITH 5-BROMO-AND 5-NITROSALICYLALDEHYDE THIOSEMICARBAZONES
(2008) Ciumacov, Iurie; Jeanneau, Erwann; Bejenari, Natalia; Țapcov, Victor; Gulea, Aurelian
The crystal structures of (5-bromosalicylidenethiosemicarbazido) aquacopper(II) sulfato(5-bromosalicylidenethiosemicarbazido)aquacuprate(II) tetrahydrate (I), (5-nitrosalicylidenethiosemicarbazido) dimethylsulfoxide(methanol)copper(II) sulfate (II), and catena(μ-thiocyanato) (5-nitrosalicylidenethiosemicarbazido)copper(II) (III) were determined. In structure I, the independent part of the unit cell contains four water molecules of crystallization and the cation-anion complex [Cu(H2O)(L)] [Cu(H2O)(L)(SO4)] containing two nonequivalent copper complexes (A and B). In these, the metal atom coordinates monodeprotonated 5-bromosalicylaldehyde thiosemicarbazone (HL) and water molecules, and in anion B also a sulfate ion. In complex ions A and B, sulfur, azomethine nitrogen, and phenolic oxygen of the salicylidene thiosemicarbazone fragment, and also water molecule form a distorted planar square around the metal atom. The axial vertex of the pyramid in anion B is occupied by the oxygen atom of the monodentate sulfate anion. In structure II, the independent part of the unit cell contains the (5-nitrosalicylidenethiosemicarbazido)dimethylsulfoxide(methanol)copper(II) complex cation and the sulfate anion. The coordination polyhedron of the central atom is a slightly distorted tetragonal pyramid whose base is formed by sulfur, azomethine nitrogen, phenolic oxygen of thiosemicarbazone, and dimethyl sulfoxide oxygen. The axial position is occupied by the methanol oxygen atom. In structure III, the copper atom coordinates 5-nitrosalicylaldehyde thiosemicarbazone and the thiocyanate ion, which combines complexes into infinite polymer chains along the [010] direction. The copper coordination polyhedron in III is a slightly distorted tetragonal pyramid whose base is formed by sulfur, azomethine nitrogen, phenolic oxygen of thiosemicarbazone, and nitrogen of thiocyanate ion, the axial vertex is occupied by sulfur of thiocyanate ion of the neighboring complex.
CRYSTAL STRUCTURE OF NITRATE TRIS (4-ALLYLTHIOSEMICARBAZIDE)- CHROMIUM(III) HYDRATE
(2016) Ciumacov, Iurie; Petrenko, Peter A.; Graur, Vasilii; Țapcov, Victor; Gulea, Aurelian
The crystal structure of nitrate tris(4-allylthiosemicarbazide)chromium(III) hydrate [CrL3](NO3)3(H2O)1.05 (I), where L is 4-allylthiosemicarbazide, is determined. The asymmetric unit of the cell of the crystal structure of I contains a complex of a chromium ion with three bidentate coordinated molecules L. The outer coordination sphere of the central atom contains a disordered water molecule and three nitrate ions. The coordination polyhedron of the chromium atom in complex I is an octahedron. In the crystal, the complexes of the compound under study are joined with each other by the outer-sphere nitrato groups into a three-dimensional branched net of hydrogen bonds.
CRYSTAL STRUCTURE OF THE ACETIC ACID SOLVATE OF N-(PROP-2-EN-1-YL)-2-(PYRID-2- YLMETHYLIDENE)HYDRAZINECARBOSELENOAMIDE
(2018) Ciumacov, Iurie; Petrenko, Peter A.; Graur, Vasilii; Țapcov, Victor; Gulea, Aurelian
The crystal structure of the acetic acid solvate of N-(prop-2-en-1-yl)-2-(pyrid-2- ylmethylidene)hydrazinecarboselenoamide (I) is determined. The asymmetric unit of the unit cell in its crystal structure contains a molecule of I and an acetic acid molecule. The molecule of I is non-planar; the angle between the mean square planes of hydrazinecarboselenoamide A(Sе1N1N2N3С1C2) and prop-2-en-1-yl (С5С6C7) moieties is 82.3°. In the crystal, the acetic acid molecules link the molecules of I in endless chains along the [010] direction.
CRYSTAL STRUCTURES OF 3-PHENYLPROPENAL THIOSEMICARBAZONE AND ITS NICKEL AND ZINC CHELATES
(2006) Ciumacov, Iurie; Samusi, Nina; Bocelli, Gabrielle; Suponițchi, Chiril; Țapcov, Victor; Gulea, Aurelian
3-Phenylpropenal thiosemicarbazone hydrate C6H 5-HC=CH-CH=N-NH-C(S)-NH2 • H2O (HL • H2O, I) and two chelates [Ni(L)2] • nCH3OH (II) and [Zn(L)2] (III) are studied by X-ray diffraction. The crystals of I are orthorhombic: a = 6.227(1) Å, b = 7.763(2) Å, c = 25.585(5) Å, β = 90°, space group P212 121, Z = 4, R = 0.0426. A nonplanar molecule of I has an E conformation. The crystals of II are triclinic: a = 6.551(2) Å, b = 10.752(3) Å, c = 10.885(3) Å, α = 64.751(5)°, β = 82.753(5)°, γ = 89.857(5)°, space group, Z = 1, R = 0.0661. In a centrosymmetric molecule of II, the central atom coordinates two deprotonated ligands L through the immine nitrogen atom and thioamide sulfur atom at the vertices of a distorted square. The crystals of III are monoclinic: a = 25.342(2) Å, b = 9.150(2) Å, c = 21.340(3) Å, α = 90°, β = 111.84(2)°, γ = 90°, space group C2/c, Z = 8, R = 0.0556. In a molecule of complex III, two deprotonated bidentate ligands L are coordinated by the zinc ion through the immine nitrogen atoms and thioamide sulfur atoms to form a distorted tetrahedron at the central atom. In both II and III, ligand L after coordination by the metal ion changes the E conformation with respect to the N(1)-C(2) bond for the Z conformation. In crystals I-III, molecules are packed to form infinite layers parallel to the planes (001) and (010)
CRYSTAL STRUCTURES OF [N′-(2- OXIDOBENZYLIDENE)-N-(PROP-2-EN-1-YL)- CARBAMOHYDRAZONOTHIOATO(2-)](1,10- PHENANTHROLINE)COPPER AND [N′-(2- OXIDOBENZYLIDENE)-N-(PROP-2-EN-1-YL)- CARBAMOHYDRAZONOTHIOATO(2-)](2,2′- BIPYRIDINE)COPPER HEMIHYDRATES
(2022) Ciumacov, Iurie; Graur, Vasilii; Ulchina, Ianina; Smaglii, Vadim; Gulea, Aurelian; Garbuz, Olga; Țapcov, Victor
The crystal structures and biological properties of [N′-(2-oxidobenzylidene)-N-(prop-2-en-1-yl)-carbamohydrazonothioato(2-)](1,10-phenanthroline)copper hemihydrate [Cu(1,10-Phen)(L)]·0.5H2O (I) and [N′-(2-oxidobenzylidene)-N-(prop-2-en-1-yl)-carbamohydrazonothioato(2-)](2,2′-bipyridine)copper hemihydrate [Cu(2,2′-BPy)(L)]·0.5H2O (II), where Н2L is 2-(2-hydroxybenzylidene)-N-(prop-2-en-1-yl)hydrazinecarbothioamide, are determined. The asymmetric unit of the unit cell in the crystal structures of I and II contains a copper complex with bidentate amine and a ligand coordinated by the azomethine nitrogen atom, the deprotonated phenolic oxygen atom, and the sulfur atom in the thiol form. The coordination polyhedron of the copper atom in compounds I and II is a distorted tetragonal pyramid. Obtained coordination compounds I and II exhibit antimicrobial and antifungal activities and have minimum inhibitory concentration and bactericidal concentration values in a range of 1.5-500 µg/mL. The study of the antioxidant activity shows that compounds I and II are less active than uncoordinated thiosemicarbazone H2L, but more active than trolox used in medical practice.
CRYSTAL STRUCTURES OF NITRATO-{2-[2-(1-PYRIDINE-2-YLETHYLIDENE)HYDRAZINE]-1,3-BENZOTHIAZOLO}AQUACOPPER AND CHLORO-{2-[2-PHENYL(PYRIDINE-2-YLETHYLIDENE)HYDRAZINE]-1,3-BENZOTHIAZOLO}COPPER
(2015) Ciumacov, Iurie; Paholnițcaia, Anastasia; Petrenko, Peter A.; Țapcov, Victor; Poirier, Donald; Gulea, Aurelian
Two crystal modifications of nitrato-{2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo}aquacopper (I and II) and two modifications of chloro-{2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo}copper (III and IV) have been synthesized and studied by X-ray diffraction. In structures I and II, the copper atoms coordinate a monodeprotonated molecule of the organic ligand, nitrate ions, and a water molecule. In crystals of I, the complexes are monomeric, whereas complexes II are linked via nitrate ions to form polymeric chains. In both structures the coordination polyhedron of the copper atom can be described as a distorted tetragonal bipyramid—(4 + 1 + 1) in I and (4 + 2) in II. These coordination polyherdra have different compositions. In structures III and IV, the metal atoms coordinate a monodeprotonated {2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazole molecule and chloride ions. In III the complex-forming ion has square-planar coordination geometry, whereas structure IV consists of centrosymmetric dimers with two bridging chlorine atoms. It was found that nitrato-{2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo}aquacopper possesses antitumor activity.
CRYSTAL STRUCTURES OF NITRATO-{4-BROMO-2- [(2-HYDROXYETHYLIMINO)METHYL]PHENOLO}- (3,5-DIBROMOPYRIDINE)COPPER AND NITRATO-{2,4-DIBROMO-6- [(2-HYDROXYETHYLIMINO)METHYL]PHENOLO}- (3,5-DIBROMOPYRIDINE)COPPER
(2006) Ciumacov, Iurie; Țapcov, Victor; Bocelli, Gabrielle; Neburger, Markus; Gulea, Aurelian
The crystal structures of nitrato-{4-bromo-2-[2-hydroxyethylimino)methyl] phenolo}-(3,5-dibromopyridine)copper (I) and nitrato-{2,4-dibromo-6-[(2- hydroxyethylimino)methyl]phenolo}-(3,5-dibromopyridine)copper (II) are determined. The crystals of compound I are orthorhombic: a = 14.157(3) Å, b = 15.420(3) Å, c = 17.494(4) Å, space group Pbca, Z = 8, R = 0.067. The crystals of compound II are monoclinic: a = 10.675 Å, b = 13.973 Å, c = 14.007 Å, β = 111.92°, space group P2 1/n, Z = 4, R = 0.0464. In the structures of compounds I and II, the copper atom coordinates, correspondingly, singly deprotonated 4-bromo-2-[(2-hydroxyethylimino)methyl]phenol and 2,4-dibromo-6-[(2- hydroxyethylimino)methyl]phenol molecules, and 3,5-dibromopyridine, and the nitrate ion. The coordination polyhedron of the copper ion in complexes I and II is a slightly distorted tetragonal pyramid. The bases of the pyramids are formed by the imine and pyridine nitrogen atoms and the phenolic and alcoholic oxygen atoms, and the axial vertices are occupied by the oxygen atoms of the monodentate nitrato groups. In the complexes under study, the six-membered metallocycles have asymmetric gauche conformation. In crystal, complexes I are united, due to the slip plane a, through bifurcate hydrogen bonds into infinite chains along the direction [100]. Complexes II in crystal form two-dimensional networks by means of hydrogen bonds.