Browsing by Author "Simonov, Iurie"

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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 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.
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 MONOPROTONATED NI(II) NITRILOTRIACETATE TETRAHYDRATE
(2004) Petrenko, Peter A.; Gdaniec, Maria; Simonov, Iurie; Stăvilă, Vitalie; Gulea, Aurelian
A Ni(II) complex of the composition Ni(HNta)·4H 2O (I) was synthesized. Its structure was found to consist of neutral mononuclear [Ni(HNta)(H 2O) 3] complexes and crystallization water molecules. The Ni atom has octahedral surrounding and is coordinated to tridentate-chelate HNta 2- ligand through the N atom and O atoms of two deprotonated acetate groups and through the O atoms of three water molecules. The structure of I was compared with those of the Zn(HNta)·4H 2O and Co(HNta)·4H 2O complexes isostructural to I. Thermogravimetric method showed that the decomposition of compound I occurs through several successive stages of dehydration, deaquation, decarboxylation, and the formation of inorganic residue.
EFFECT OF THE NATURE OF THE ANION ON THE COMPOSITION AND STRUCTURE OF COBALT COMPLEX WITH MONOETHANOLAMINE
(2013) Cotovaia, Aliona; Șova, Sergiu; Melnic, Elena; Simonov, Iurie; Gulea, Aurelian; Pahonțu, Elena
A number of products formed in reactions of cobalt(II) salts with monoethanolamine (HEtm) in a neutral medium were synthesized and studied. X-Ray diffraction study showed that the nitrate and acetate form the dimers [Co(HEtm)3][Co(Etm)3](NO3)3 and [Co(HEtm)3][Co(Etm)3](CH3COO)3 · 8H2O, respectively. In chloride solutions, cobalt is partially oxidized to give the trinuclear complex [CoII{Co III(Etm)3}2]Cl3 · H 2Etm · 2H2O. The reaction of the chelate [Co(Etm)3] · 3H2O with nitric acid is accompanied by complete protonation of the coordinated aminoethanolate ions, and the reaction with formic acid involves complete replacement of the coordinated ligand by acid residue anions and water molecules to give the coordination polymer {Co2(μ-HCOO)4(H2O)4} n .
HETEROMETALLIC COMPOUNDS WITH THE BINUCLEAR COMPLEX ANION [CR2 (OH)(AC)(NTA)2 ]2– : SYNTHESIS AND STRUCTURE
(2009) Ciornea, Victor; Șova, Sergiu; Novițchi, Ghenadie; Ganju, Dumitru; Cajeva, Olga; Gulea, Aurelian; Simonov, Iurie
Heterometallic compounds BaCr2(OH)(Ac)(Nta)2 • 4H2O (I) and [Fe(L)3][Cr2(OH)(Ac)(Nta) 2] • nH2O (L is Bipy (II) and Phen (III); Bipy is, αα′-bipyridine, Phen is o,o′-phenanthroline, Ac - is acetate ion, Nta is nitrilotriacetate ion; n = 8 (II) and 6.25 (III)) are synthesized. According to the X-ray diffraction data, compounds II and III have ionic structures built of the isolated complex cations [Fe(L) 3]2+, binuclear complex anions [Cr2(OH)(Ac) (Nta)2]2-, and crystallization water molecules. The magnetic properties of compounds II and III in the interval from 2 to 300 K confirm assumptions on the diamagnetic character of [Fe(L)3] 2+ and indicate the antiferromagnetic interaction between the chromium atoms in the dimeric fragment [Cr2(OH)(Ac)(Nta) 2]2-.
NEW COMPLEXES OF TRIS(2-AMINOETHANOLATO-O,N)COBALT(III) SULFATES: SYNTHESIS AND STRUCTURE
(2009) Cotovaia, Aliona; Șova, Sergiu; Simonov, Iurie; Gulea, Aurelian
The reaction of [Co(Etm)3] • 3H2O (I) with sulfuric acid affords [Co(HEtm)3]2(SO4) 3 • 4H2O (II). The change in the synthesis procedure (the direction interaction of cobalt(II) sulfate with β-aminoethanol (HEtm)) makes it possible to isolate [Co(HEtm)3](SO 4)(HSO4) • H2O (III) and {[Co(HEtm) 3][Co(Etm)3]}2(SO4)3 • 7.75H2O (IV). The X-ray diffraction analyses of compounds II-IV show that all of them are of the ionic type. In compounds II and III, the ionic structure consists of the [Co(HEtm)3]3+ cations and sulfate anions in a ratio of 2: 3 and 1: 2, respectively. The basic difference in compounds II and III is the different degrees of deprotonation of the acid residues. In complex II, two anions SO 4 2- are doubly deprotonated. In complex III, of the four anions found in the independent part of the unit cell of the sulfate anion two anions are monodeprotonated. In structure IV, two crystallographically independent complexes [Co(HEtm) 3]3+ and [Co(Etm)3] are joined into a dimer through the O-H⋯O hydrogen bonding.
NEW CRYSTAL FORMS OF TRIS(2-AMINOETHANOLATO-O,N)COBALT(III): STRUCTURES AND PROPERTIES
(2006) Cotovaia, Aliona; Șova, Sergiu; Simonov, Iurie; Roșu, Tudor; Sandu, Ion; Gulea, Aurelian
Crystal forms of cobalt(III) tris(2-aminoethanolate) hydrates, i.e., red cubic crystals of the composition fac-[Co(NH2CH2CH 2O)3] • 5.44H2O (fac-I • 5.44H 2O) and blue prismatic crystals of the composition mer-[Co(NH 2CH2CH2O)3] • 3H2O (mer-I • 3H2O) were studied by the 59Co, 13C NMR and X-ray diffraction methods. It was found that mer-[Co(NH2CH2CH2O)3] • 3H 2O (mer-I • 3H2O) is a new pseudopolymorphic modification of fac-[Co(NH2CH2CH2O) 3] • 3H2O (fac-I • 3H2O), while fac-I • 3H2O represents a new polymorphic modification of the complex mer-[Co(NH2CH2CH2O)3] • 3H2O (mer-I • 3H2O) described previously. The comparative analysis of the spectra revealed dynamic equilibrium between these geometric isomers; the fac-isomer is stable in aqueous solutions.
SYNTHESIS AND STRUCTURE OF HETEROMETALLIC CHROMIUM(III) COMPLEXES WITH ETHYLENEDIAMINETETRAACETIC ACID
(2005) Ciornea, Victor; Filippova, Irina; Gulea, Aurelian; Șova, Sergiu; Borta, A.; Simonov, Iurie
The complexes [M(Tsc)2][Cr(Edta)]2, where M is Ni, Cu; Tsc is thiosemicarbazide; Edta4- is the ethylenediaminetetraacetate anion, were synthesized and characterized by X-ray diffraction. The ionic structures are composed of the [M(Tsc)2] 2+ cations and [Cr(Edta)]- anions with a component ratio of 1 : 2. The cation has a distorted trans-square coordination. The carboxyl groups of the H4Edta molecule are deprotonated and the ligand is attached to the Cr atom in the hexadentate chelating mode. The cations and anions are linked by a system of hydrogen bonds.
SYNTHESIS AND STRUCTURE OF {M-OXALATO-BIS[ETHYLENEDIAMINETETRAACETATO- BISMUTHATO(III)]}PENTAAMMINETHIOCYANATOCOBALT(III) DODECAHYDRATE, [CO(NH3)5NCS]2[(EDTA)BI(M-C2O4)BI(EDTA)] • 12H2O
(2000) Stăvilă, Vitalie; Gdanec, M.; Șova, Sergiu; Simonov, Iurie; Gulea, Aurelian; Vignacourt, Jean-Pierre
A heterometallic complex of cobalt(III) and bismuth(III), [Co(NH3)5NCS]2[(Edta)Bi(μ-C2O4)Bi(Edta)] · 12H2O, was synthesized and studied by X-ray diffraction analysis. The crystals are monoclinic, a = 12.792(3) Å, b = 9.792(2) Å, c = 22.945(5) Å, β = 92.92(3)°, P(calcd) = 1.970 g/cm3, space group P21/c, Z = 4. The complex has an isle structure composed of [(Edta)Bi(μ-C2O4)Bi(Edta)]4- and [Co(NH3)5NCS]2+ complex ions and molecules of crystallization water. The Edta4- ligand functions as a hexadentate chelating (2N + 40) agent, while the oxalate ion acts as a bridging ligand. The thiocyanate ion is coordinated to cobalt(III) through the N atom, while the cation interacts with the anion via the Bi-S contact (3.571 Å). Hence, the coordination polyhedron of Bi can be regarded as a tricapped trigonal prism. It was shown that thermolysis of the complex proceeds in several stages, viz., the deaquation, deamination, and pyrolysis of its ligands.
SYNTHESIS AND STUDY OF HETEROMETALLIC CO–BI COMPOUNDS BASED ON ETHYLENEDIAMINETETRAACETIC ACID. CRYSTAL AND MOLECULAR STRUCTURES OF [CO(DH)2(O -NH2C6H4CH3)2]2[BI2(M-EDTA)2(H2O)2] • 10H2O (DH2 IS DIMETHYLGLYOXIME)
(2002) Stăvilă, Vitalie; Gulea, Aurelian; Șova, Sergiu; Gdanec, M.; Simonov, Iurie
Compounds of the [Co(DH)2A2](BiEdta)·6H 2O type (where DH is the monodeprotonated dimethylglyoxime -ON=C(CH3)-(CH3)C=NOH; A is the o-, m-, or p-toluidine; and Edta is the ethylenediaminetetraacetate(4-) ion) were synthesized and studied. The composition and structures of the complexes were determined from their UV and 1H NMR spectra and from X-ray diffraction data. The isomer [Co(DH)2(o-NH2C 6H4CH3)2]2[Bi 2(μ-Edta)2(H2O)2]·10H 2O was structurally characterized using X-ray diffraction analysis. The crystals are triclinic: a = 12.153(2) Å, b = 12.824(3) Å, c = 16.215(3) Å, α = 67.73(3)°, β = 86.18(3)°, γ = 66.96(3)°, space group P1̄ , ρ(calcd) = 1.719 g/cm3, Z = 4. The structure is composed of complex binuclear [Bi2(μ-Edta) 2(H2O)2]2- anions, [Co(DH) 2(o-NH2C6H4CH3) 2]+ cations, and molecules of crystallization water. The Edta4- anion chelates with the Bi atom in a hexadentate manner (N2O4); the fifth O atom functions as a bridging ligand. The bismuth coordination polyhedron can be regarded as a strongly distorted antiprism. In the octahedral cation, the Co(III) atom coordinates four N atoms of two DH ligands (average Co-N 1.897 Å) and two N atoms of two o-toluidine molecules (Co-N 2.023 Å). Thermolysis of the complexes studied was found to proceed in several successive steps, namely, the deaquation, deamination, and pyrolysis of the ligands.