Magnetic studied of a binuclear Cu(II) complex constructed from Cu(II) macrocyclic complex

A new binuclear copper(II) compound [(CuL)₂(Tpha)](ClO₄)₂ · 4H₂O (I), where L = 1,3,6,9,11,14-hexaazatricyclo[12.2.1.1^6,9]octadecane, Tpha = terephthalate dianion, has been constructed and structurally characterized by X-ray crystallography. Crystal analysis denotes that complex I crystallizes in the monoclinic system, space group P2₁/c with a = 11.115(2), b = 13.185(3), c = 16.184(3) Å and β = 105.68(3)°. Magnetic measurements confirm that I present an antiferromagnetic interaction between the paramagnetic ions.     

Dicopper(II) Assembly Containing the Tetrameric Cluster of Water Constructed from Terephthalate Dianion and Copper(II) Macrocyclic Fragment

To utilized a mononuclear fragment of [Cu(L)Cl]ClO₄ (1) and TPHA bridged-ligand as building block by self-assembly technology, a new dinuclear copper(II) compound [(CuL)₂(μ-TPHA)](ClO₄)₂ · 4H₂O (2), where L = 1,3,6,9,11,14-hexaazatricyclo[12.2.1.1^6,9]octadecane, TPHA = terephthalate dianion, has been constructed and structurally characterized by X-ray crystallography. Crystal analyses denotes that crystal water molecules interact with each other give rise to a tetrameric cluster of water, which by sharing dinuclear units result in a 1D chain structure. Complex 2 crystallizes in monoclinic, space group P2₁/c, with a = 11.1586(14), b = 13.2240(16), c = 16.241(2) Å and β = 105.636(2)°. Magnetic measurements confirm that 2 present an antiferromagnetic interaction between the paramagnetic ions.     

Complexes of Cu(II) and Co(II) nitrates with 3-Phenyl-5,5-dimethyl-5,6-dihydro-1,2,4-triazolo[3,4-a]isoquinoline

Complexes of Cu(II) and Co(II) nitrates with 3-phenyl-5,5-dimethyl-5,6-dihydro-1,2,4-triazolo[3,4-a]isoquinoline (L⁰) of the composition [CuL ₂ ⁰ (NO₃)₂] (I) and [CoL ₂ ⁰ (NO₃)₂] · CH₃CN (II) are synthesized and their crystal structures are determined by X-ray diffraction. The L⁰ ligand is coordinated to the metal atoms through the N atom in position 2 of triazole fragment. The coordination polyhedron of the Cu(II) atom is a square with two additional axial vertices, while that of the Co(II) atom is a tetrahedron with two additional vertices. The NO ₃ ^? groups in the structures of I and II perform similar anisobidentate function. Complexes I and II are studied by IR and electronic spectroscopy.     

Cu(I) cloride complexes with 4,5-(2-pyridylethylene)dithio-1,3-dithiol-2-thione and triphenylphosphine

Heteroligand binuclear complexes of CuCl with triphenylphosphine and 5-pyridine-2-yl-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione (L¹) of the compositions [CuCl(PPh₃)(L¹)]₂ (I) and [CuCiL¹]₂ (II) are synthesized and studied by X-ray diffraction method. Crystals I are monoclinic; space group P2₁/n, a=8.9520(18) Å, b=18.926(4) Å, c=16.841(3) Å, β=94.96(3)°, Z=2. The Cu(I) atom has a quasi-tetrahedral surrounding involving the tetraphenylphosphine P atom, the pyridyl N atom of the molecule L¹, and two bridging Cl atoms. Crystals II are monoclinic; space group P2₁/c, a=9.3520(19) Å, b=8.1490(16) Å, c=18.660(4) A, β = 104.43(3)°, Z = 2. Both L¹ ligands in complex II act as bridges. The Cu(I) atom also has a quasi-tetrahedral surrounding formed by the Cl atoms, the pyridyl N atoms and thiol S atom of one L¹ ligand, and the thione S atom of the second L¹ ligand. Similar binuclear complexes with the bridging function of the L¹ ligand were also detected in a solution of II by the ESI method.     

Synthesis, characterization, and X-ray crystal structures of copper(II) and nickel(II) complexes with Schiff base

New copper(II) complexes, [Cu₂L¹L²] · ClO₄ (I) and [Ni(L³)₂] (II), where L¹ is the monoanionic form of 2-[1-(2-emthylaminoethylimino)ethyl]phenol, L² is the dianionic form of N,N′-ethylene-bis(2-hydroxyacetophenonylideneimine), L³ is the mono-anionic form of 2-(1-iminoethyl)phenol, were prepared and characterized using elemental analysis, FT-IR spectroscopy, and X-ray single-crystal diffraction. In complex I, the Cu(1) atom is coordinated by the NNO tridentate ligand L¹ and the two phenolate O atoms of L², forming a square pyramidal geometry. The Cu(2) atom in complex I is coordinated by the NNOO tetradenate ligand L², forming a square planar geometry. The Ni atom in complex II is coordinated by two phenolate O and two imine N atoms from two ligands L³, forming a square planar geometry. In the crystal structure of I, the perchlorate anions are linked to the dinuclear copper(II) complex cations through intermolecular N-H...O hydrogen bonds. In the crystal structure of II, the mononuclear nickel complex molecules are linked through intermolecular N-H...O hydrogen bonds, forming a trimer.     

Comparative investigation of the copper(II) complexes of (R)-, (S)- and (R,S)-1-phenyl-N,N-bis(pyridine-3-ylmethyl)ethanamine along with the related complex of (R,S)-1-cyclohexyl-N,N-bis(pyridine-3-ylmethyl)ethanamine. Synthetic, magnetic, and structural studies

The interaction of the enantiopure (R)- and (S)-1-phenyl-N,N-bis(pyridine-3- ylmethyl)ethanamine ligands, R-L ¹ and S-L ¹ , with copper(II) chloride followed by addition of hexafluorophosphate resulted in the isolation of the corresponding enantiomeric complexes [Cu(R-L ¹ )Cl](PF₆) (1), [Cu(S-L ¹ )Cl](PF₆) (2) and [Cu(S-L ¹ )Cl](PF₆)??0.5Et₂O (3), in which dimerization occurs through two long Cu??????Cl interactions, the ??-chloro bridges being thus strongly asymmetric. The organic ligand is bound to the metal centre via its N₃-donor dipyridylmethylamine fragment in a planar fashion, such that each copper centre is in a square planar environment (or distorted square pyramidal with a long axial bond length if the additional interaction is considered). When R,S-L ¹ was employed in a parallel synthesis, the similar racemic complex [Cu(R,S-L ¹ )Cl](PF₆)??0.5MeOH (4) was obtained, in which the L ¹ ligands in each dimeric unit have opposite hands. In contrast to the complexes of L ¹ , the reaction of Cu(II) chloride with the related ligand, (R)-1-cyclohexyl-N,N-bis(pyridine-3-ylmethyl)ethanamine (R-L ² ), yielded the mononuclear complex [Cu(R,S-L ² )Cl₂] (5), displaying a distorted square pyramidal coordination geometry. The structure of this product along with its corresponding circular dichroism spectrum revealed that racemisation of the starting R-L ² ligand has occurred under the relatively mild (basic) conditions employed for the synthesis. A temperature-dependent magnetic studies of the complexes 1, 2 and 5 indicate that a week ferromagnetic interaction is operative in each dicopper core in 1 and 2 with 2J?=?1.2?cm^?1. On the other hand, a week antiferromagnetic intermolecular interaction is operative for 5.     

Copper(II) cyanido-bridged bimetallic nitroprusside-based complexes: Syntheses, X-ray structures, magnetic properties, Fe Mössbauer spectroscopy and thermal studies

Three heterobimetallic cyanido-bridged copper(II) nitroprusside-based complexes of the compositions [Cu(tet)Fe(CN)₅NO]·H₂O (1), where tet=N,N′‐bis(3-aminopropyl)ethylenediamine, [Cu(hto)Fe(CN)₅NO]·2H₂O (2), where hto=1,3,6,9,11,14-hexaazatricyclo[12.2.1.1^6,9]octadecane and [Cu(nme)₂Fe(CN)₅NO]·H₂O (3), where nme=N-methylethylenediamine, were synthesized and characterized by elemental analyses, ⁵⁷Fe Mössbauer and FTIR spectroscopies, thermal analysis, magnetic measurements and single-crystal X-ray analysis. The products of thermal degradation processes of 2 and 3 were studied by XRD, ⁵⁷Fe Mössbauer spectroscopy, SEM and EDS, and they were identified as mixtures of CuFe₂O₄ and CuO.     

Copper(II), iron(III) and cobalt(III) complexes of the pendent-arm cyclam derivative 6,6,13-trimethyl-13-amino-1,4,8,11-tetraazacyclotetradecane

The interaction of Cu(II), Fe(III) and Co(III) with 6,6,13-trimethyl-13-amino-1,4,8,11-tetraazacyclotetradecane (L ³ ) incorporating a pendent amine group has led to isolation of the new octahedral complexes [Cu(HL ³ )(ClO₄)₂]Cl·H₂O (1), [Fe(L ³ )Cl](S₂O₆)·H₂O (2), [Co(L ³ )Cl](ClO₄)_1.5Cl_0.5·0.25H₂O (3), [Co(HL ³ )Cl₂](ClO₄)₂·H₂O (4) and [Co(L ³ )Cl]₂(S₂O₄)(ClO₄)₂ (5). In (1) the copper ion occupies the macrocyclic cavity of protonated (–NH₃ ⁺) L ³ which is present in its trans-III configuration; weakly bound ClO₄ ^? ligands occupy the axial positions. The X-ray structure of (2) showed that Fe(III) occupies the N₄-macrocyclic cavity of L ³ in a trans-III configuration, with the pendent amine group binding in an axial position. The remaining axial position is occupied by a Cl^? ligand. Chromatography of the product obtained from the reaction of Na₃[Co(CO₃)₃] with L ³ yielded three fractions. Fraction 1 yielded crystals (3) composed of three crystallographically independent species incorporating cations of type [Co(L ³ )Cl]²⁺ with very similar structures; in each case the macrocyclic ring nitrogens of L ³ are bound to the Co(III) in an asymmetric cis-fashion. Fraction 2 yielded the trans-III octahedral cationic complex (4) incorporating L ³ in its protonated form. The Co(III) complex (5) from fraction 3 shows a different coordination arrangement to the products from fractions 1 or 2. The macrocyclic ring coordinates in its trans-III form, but the axial sites in this case are occupied by the pendent-NH₂ group and a Cl^? ligand.     

Ni(II) complexes with optically active bis(menthane), pinano-para-menthane ethylenediaminodioximes and pinano-para-menthane, bis(pinane) propylenediaminodioximes: Synthesis, structures, and properties

Reactions of Ni(NO₃)₂ · 6H₂O) in EtOH(iso-PrOH) with optically active bis(menthane) ethylene-diaminodioxime (H₂L¹), pinano-para-menthane ethylenediaminodioxime (H₂L²), pinano-para-menthane propylenediaminodioxime (H₂L³) and bis(pinane) propylenediaminodioxime (H₂L⁴) were used to synthesize [Ni(H₂L¹)NO₃[NO₃ · 2H₂O (I), [Ni(HL²)]NO₃ (II), [Ni(HL³)]NO₃ (III), and [Ni(HL⁴)]NO₃ (IV). X-ray diffraction study of paramagnetic complex I (μ_eff = 3.04 μB and diamagnetic complexes II and III revealed their ionic structures. A distorted octahedral polyhedron N₄O₂ in the cation of complex I is formed by the N atoms of tetradentate cycle-forming ligand, i.e., the H₂L¹ molecule, and the O atoms of the NO ₃ ^? anion acting as a bidentate cyclic ligand. In the cations of complexes II and III, containing a pinane fragment, the coordination core NiN₄ has the shape of a distorted square formed on coordination of tetradentate cycle-forming ligands, i.e., anions of the starting dioximes. The structure of diamagnetic complex IV is likely to be similar to the structures of complexes II and III.     

Synthesis of binuclear complexes of PdCl2 with chiral ethylenediamine dioxime (H2L1), piperazine dioxime (H2L2), and propylenediamine dioxime (H2L3), the derivatives of the natural monoterpenoid (R)-(+)-limonene. The crystal structures of [Pd2(H2L1)Cl4] and [Pd2(H2L2)Cl4]

The diamagnetic complexes [Pd₂(H₂L¹)Cl₄] (I), [Pd₂(H₂L²)Cl₄] (II), and Pd₂(H₂L³)Cl₄(III) with chiral ligands derived from the natural monoterpenoid (R)-(+)-limonene are obtained (H₂ L¹ is ethylenediamine dioxime, H₂L² is piperazine dioxime, and H₂L³ is propylenediamine dioxime). According to X-ray diffraction data, the crystal structures of complexes I and II are composed of binuclear acentric molecules. The coordination polyhedra PdN₂Cl₂ are trapeziums (squares distorted in a tetrahedral manner) made up of two N atoms of the tetradentate bridging cyclic ligands H₂L¹ and H₂L² and two Cl atoms. The fragments PdCl₂ are trans in the complexes. The ¹³C and ¹H NMR spectra of complexes I and II in CDCl₃ also suggest their binuclear structures.     

Structural diversity of two novel complexes of Co(II) with bis-triazole ligand: From one-dimensional chain to two-dimensional porous network

Using two novel bis-triazole ligands, 2,6-bis(1,2,4-triazole-4-yl)pyridine (L¹) and 1,6-bis(1,2,4-triazole-1-yl)hexane (L²), one novel one-dimensional (1D) chain polymer [Co(NCS)₂(L¹)₂] _n (I) and one two-dimensional (2D) coordination polymer [Co(NCS)₂(L²)₂] _n (II) have been synthesized and structurally characterized. The crystal crystallizes in the triclinic system for I, space group $P\bar 1$ , a = 7.879(6), b = 8.830(7), c = 9.837(8)Å, α = 70.230(11)°, β = 115.474(6)°, γ = 85.591(12)°, Z = 1. The crystal crystallizes in the mo-noclinic system for II, space group $P\bar 1$ , a = 7.879(6), b = 8.830(7), c = 9.837(8) α = 70.230(11)°, β = 115.474(6)°, γ = 85.591(12)°, Z = 1. The structural diversity of these two new Co(II) complexes vary from 1D chain to 2D porous supramolecular network, which may be ascribed to ligand directing effects under similar synthetic conditions (L¹ contains rigid pyridine spacers while L2 contains flexible hexane spacers).     

A novel hexaaza macrocyclic complex [CuL](ClO<Subscript>4</Subscript>)<Subscript>2</Subscript>

A novel N₄-planar Cu(II) macrocyclic fragment, namely, [CuL](ClO₄)₂ (I) (L = 4-methyl-1,3,6,8,11,14-hexaazatricyclo[12.2.1.1^8,11)octadecane has been prepared from a simple template condensation reaction and structurally characterized for the first time. The complex of I crystallizes in the monoclinic system of space group P2₁/c with unit cell parameters: a = 17.124(10), b = 9.255(5), c = 14.053(8) Å and β = 111.262(7)°.     

Synthesis,characterization,structures and magnetic property of chiral oxalate-bridged dicopper(Ⅱ) complexes

The oxalato-bridged dicopper(II) complexes [Cu2(μ-ox)(LRR)2(H2O)2(ClO4)2] (1),[Cu2(μ-ox)(LRR)2(CH3COCH3)2(ClO4)2](1a),[Cu2(μ-ox)(LSS)2(H2O)2(ClO4)2] (2) and [Cu2(μ-ox)(LRR)(LSS)2(CH3COCH3)2(ClO4)2] (3) [LRR = (8R,10R)-(-)-[4,5]-pineno2,2′-bipyridine,LSS = (8S,10S)-(+)-[4,5]-pineno-2,2′-bipyridine;ox2= oxalate] were first prepared.A possible mechanism for the formation of the chial dicopper(II) complexes was proposed.Based on elemental analysis,conductance measurement,UV-Vis spectra,CD spectra and X-ray single-crystal diffraction,the oxalato-bridged structures of 1 and 2 were deduced to adopt two Cu(II) ions and the bridged oxalate lying in the nearly same plane.The crystal structures of 1a and 3 reveal that the coordination geometry around each Cu(II) ion is an elongated and distorted octahedron and two axial solvent molecules and two perchlorate ions are anti to each other respectively in both binuclear molecules.The solution CD spectra of 1 and 2 in the visible d-d range show very weak Cotton effects with peaks at 588 and 779 nm,which are approximately of mirror image,suggesting the optical activities may be derived from the vicinal effects of the chiragenic centers at the pinene group of LRR and LSS,respectively.Complex 1 has been characterized by variable-temperature magnetic susceptibility and the data was least-square fitted to the Blenaey-Bowers equation.The exchange integral J was found to be -338.41(4) cm-1,indicating a strong antiferromagnetic interaction between two copper(II) ions.     

Synthesis, crystal structures, and properties of inorganic-organic hybrid complexes constructed from copper(II) macrocyclic fragment

Reaction of a macrocyclic copper(II) complex [Cu(L)](ClO₄)₂ · 3H₂O (I) (L = 1,3,10,12,16,19-hexaazatetracyclotetracosane) with a hexapod carboxylate ligand H₆TTHA (H₆TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetic acid) and a tripod carboxylate ligand H₃TATB (H₃TATB = 4,4′,4″-S-triazine-2,4,6-triyl-tribenzoic acid) yielded two mononuclear copper(II) complexes [Cu(L)][H₄TTHA] · 4H₂O (II) and [Cu(L)][HTATB] · 4H₂O (III). The complexes I–III have been structurally characterized. The crystal structures of complexes II and III show the copper(II) ion has a distorted pentacoordinate square-pyramidal geometry with two secondary and two tertiary amines from the macrocyclic complex [Cu(L)]²⁺ and one oxygen atom from the carboxylate ligand group at the axial position. The UV-Vis spectra are utilized to discuss the hydrolysis of the complex II.     

Copper(II) Complexes with Chiral Ligands Containing Fragments of Monoterpenoids and Amino Acid Esters

Complexes [CuL¹Cl₂] (I), [CuL²Cl₂] · EtOH (II), and Cu₂L³Cl₄ (III) containing esters of the N-derivatives of optically active amino acids based on (+)-3-carene (L¹, L²) and (?)-α-pinene (L³) are synthesized. The crystal and molecular structures of compounds I and II are determined by X-ray diffraction analyses (CIF files CCDC nos. 1560071 (I), 1560072 (II)). The crystal structure of compound I consists of mononuclear complex molecules. In the structure of compound II, the unit cell contains two crystallographically independent molecules of mononuclear complex [CuL²Cl₂] and two EtOH molecules. Ligands L¹ and L² perform the tridentate-chelating function by the N atoms of the NH and NOH groups and by the O atom of the C=O group. In compounds I and II, the coordination polyhedra Cl₂N₂O of the Cu atoms are trigonal bipyramid. According to the data of IR and electronic spectroscopy, binuclear complex III has similar coordination polyhedra. The experimental values of μ_eff for compounds I, II, and III at 300 K are 1.93, 1.88, and 2.71 μB. For complex III, the μ_eff(T) dependence in a range of 2–300 K indicates a weak ferromagnetic exchange interaction.     

Synthesis,crystal structures,and antibacterial activities of Schiff base nickel(II) and cadmium(II) complexes with tridentate Schiff bases

Reaction of tridentate Schiff bases with nickel and cadmium salts in methanol afforded two new mononuclear complexes, [Ni(L¹)₂] (I) and [Cd(L²)₂] (II), where L¹ and L² are the anions of 2-bromo-4-chloro-6-[(3-dimethylaminopropylimino)methyl]phenol (HL¹) and 2-bromo-4-chloro-6-[(3-morpholin-4-ylpropylimino)methyl]phenol (HL²), respectively. The complexes were characterized by singlecrystal X-ray diffraction (CIF files CCDC nos. 1428653 (I) and 1428654 for (II)), FT-IR, and elemental analysis. Complex I crystallizes in the monoclinic space group P2 ₁/c, with a = 8.8216(8), b = 14.0424(8), c = 11.8687(12) Å, β = 111.238(2)°, V = 1370.4(2) ų, Z = 2. Complex II crystallizes in the monoclinic space group P2 ₁/n, with a = 9.6774(4), b = 15.8970(6), c = 20.3144(7) Å, β = 90.408(2)°, V = 3125.1(2) ų, Z = 4. The metal atoms in the complexes are coordinated by two tridentate Schiff base ligands, forming octahedral coordination. The free Schiff bases and the complexes were assayed for antibacterial activities. Both complexes are more active against the bacteria than the free Schiff bases. Complex II has the MIC value of 0.39 μg mL^–1 against Bacillus subtilis.     

Synthesis and crystal structures of two new Schiff base cobalt(II) and nickel(II) complexes

The Schiff base ligand (HL) obtained from phenylmethanamine and 5-methoxysalicylaldehyde are used as ligands for Co(II) and Ni(II) resulting in complexes [Co(L)₂] (I) and [Ni(L)₂] (II), and their solid state structures were determined by X-ray crystallography. In both complexes, weak interactions play an important role in the molecular self-assembly. Complex I was stacked up to the 2D layers by C-H…O hydrogen bonds and C-H…π interactions. In contrast, complex II was extended into 2D sheet by C-H…O hydrogen bonds, the C-H…π interactions, and edge-to-face interactions.     

Synthesis, characterization and catalytic activity of three palladium(II) complexes containing Schiff base ligands

Three new Pd(II) complexes of Schiff base ligands, namely, [Pd₄(L¹)₄] (1), [Pd₂(L²)₂Cl₂] (2) and [Pd(L³)₂Cl₂] (3) [HL ¹ ?=?N-(benzylidene)-2-aminophenol; L ² ?=?N-(2,4-dichlorobenzylidene)-2,6-diethylbenzenamine, L ³ ?=?4-(2,4-dichlorobenzylide-neamino)phenol] have been synthesized using solvothermal methods and characterized by elemental analysis, spectroscopy and single crystal X-ray diffraction. The crystal structures of the free ligands were also determined. The ??-oxygen-bridged tetranuclear cyclometallated Pd(II) complex (1) contains four nearly planar units, in which Pd^II is four-coordinate. Complex 2 is a ??-chloro-bridged dinuclear cyclometallated Pd(II) complex, whereas complex 3 is mononuclear. The Heck reactions of bromobenzene with acrylic acid catalyzed by complexes 1?C3 have also been studied.     

Manganese(II) and copper(II) complexes based on pentafluorobenzoate: interaction of fluorine in solid state

The synthesis and characterization of Mn(II) and Cu(II) complexes with the general formula [Mn(Phen)₂(Pfbz)₂](Hpfbz) (I) and [Cu₂(Bipy)₂(Pfbz)₄] (II) (Phen = 1,10-phenanthroline, Bipy = 2,2′-bipyridine, Pfbz = pentafluorobenzoate) are reported. I crystallizes in triclinic crystal system, space group {tiP}1 with a = 9.755(1), b = 11.302(1), c = 20.064(2) Å, α = 95.799(2)°, β = 90.176(2)°, γ = 113.993(2)°, and Z = 2. Complex II crystallizes in triclinic crystal system, space group P1 with a = 9.661(1), b = 9.951(1), c = 12.891(1) Å, α = 102.943(2)°, β = 98.972(2)°, γ = 96.746(2)°, and Z = 1. Of particular interest, intricate C-H…F and F…F interactions in the two crystals play important role in the formation of three dimensional supramolecular networks. F(lp)…π (lp = lone pair) interaction is recognized in the solid-state structure of II.     

Hydrothermal synthesis, crystal structures, and properties of two Co(II) complexes based on 4-bromoisophthalic acid and N-donor ligands

Two new Co(II) complexes, [Co₂(H₂O)(Bipy)₂(Bript)₂] _n (I) and [Co(H₂O)(Phen)(Bript)] · H₂O (II), where H₂Bript = 4-bromoisophthalic acid, Bipy = 2,2??-bipyridine, and Phen = 1,10-phenanthroline, have been synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. Complex I has binuclear units in which two Co²⁺ ions are bridged by two carboxylate groups and a coordinaiod-water molecule, and the binuclear units are connected by Bript to generate a 1D helical chain. These 1D helical chains are further linked by ????? stacking interactions to form a 3D supramolecular network, while complex II has a 2D layer motif. In I and II, there exists extensive hydrogen bonding interactions. The thermal behavior of the two corresponding complexes have briefly been investigated.