Reaction of copper(II) cysteinate with thiosemicarbazide: Crystal structure of a complex of copper(II) thiocyanate with thiosemicarbazide

The reaction of copper(II) cysteinate with thiosemicarbazide (TSC) in water was found to yield complex of copper(II) thiocyanate of the [Cu(TSC)₂(SCN)₂] composition, whose crystal structure was determined by X-ray crystallography. Crystals of the complex are triclinic with a = 6.040 Å, b = 7.112 Å, c = 8.276 Å, α = 91.34°, β = 101.72°, Γ = 114.83°, Z = 2, space group \(P\bar 1\). Structural units of the complex are [Cu(TSC)₂]²⁺ centrosymmetric cations and (SCN)^? anions linked by hydrogen bonds (HB), as well as by electrostatic and π-π stacking interactions. The coordination polyhedron of Cu atoms is a square completed to bipyramid; the bonds Cu(1)-N(3), Cu(1)-S(1), and Cu(1)-S(2) are 2.002 Å, 2.303 Å, and 3.015 Å, respectively.     

Synthesis of a novel copper(II) complex and its crystal structure

One novel chiral copper(II) complex was successfully synthesized from the reaction of chiral 1,3-thiazolidine-2-thione ligand with CuCl₂ in dichloromethane in the presence of Et₃N and DMAP at room temperature. Its unique crystal structure was unambiguously disclosed by X-ray analysis. The crystal is tetragonal, space group I4(1), space group a=15.0875(11), b=15.0875(11), c=19.362(3) Å, =90, β=90, γ=90°, V=4407.4(8) ų, Z=8, ρ_calc=1.639 mg cm⁻³.     

Synthesis and crystal structure of hydrated cation-anion nickel(II) thiosemicarbazide and nickel(II) malonate dihydrate complex

A crystal of Ni(HL)₂[Ni(Malon)₂(H₂O)₂]₂ · 3.51H₂O (I), which is built of [Ni(HL)₂]₂₊ cations (HL is thiosemicarbazide), [Ni(Malon)₂(H₂O)₂]_2? anions (H₂ Malon is malonic acid), and molecules of crystal water, has been synthesized and studied by IR spectroscopy, thermogravimetry, and X-ray diffraction. Structural units of complex I are linked by electrostatic interactions and numerous hydrogen bonds. The unit cell parameters b = 7.233(1) Å, c = 24.426(5) Å, β = 127.98(3)°, space group C2/c, Z = 8. The polyhedron of the nickel atom in [Ni(HL)₂]₂₊ cations is a cis-square that is slightly distorted within ～10°. Ligands HL are bidentately chelately coordinated (via N and S) to the nickel atom with the closure of near planar five-membered chelate rings. The malonate groups in [Ni(Malon)₂(H₂O)₂]^2? anions are bidentately chelately coordinated with the formation of six-membered non-planar chelate rings. The coordination of the central atom is complemented to an octahedron with two H₂O molecules. The bond lengths in cations are 1.924(4) and 1.912(4) Å (Ni-N) and 2.144(1) and 2.150(2) Å (Ni-S), and the bond lengths in anions are 2.003–2.046(3) Å (Ni-O) and 2.113(4) and 2.122(3) Å (Ni-O(w)).     

Synthesis and crystal structure of the copper(II) valerate complex with nicotinamide

A coordination compound of copper(II) valerate with nicotinamide, [CuL(C₄H₉COO)₂]₂ (I), has been synthesized, and its crystal structure has been determined by X-ray crystallography. The crystals of I are triclinic: a = 9.1245(9) Å, b = 9.8572(6) Å, c = 11.0944(9) Å, α = 73.51(1)°, β = 79.917(6)°, γ = 72.161(7)°, Z = 2, space group $P\bar 1$ . In the centrosymmetric binuclear molecule of I, the copper atoms (Cu...Cu′, 2.621 Å) are linked through four bidentate chelating valerate ligands (av., Cu-O 1.969 Å). The coordination polyhedron of the Cu atom is a tetragonal pyramid with the nitrogen atom of the pyridine ring in the apical position at a longer distance (Cu-N, 2.190 Å).     

Self-assembly and crystal structure of a three-dimensional copper(II) complex

A copper(II) complex of a sulfonate derivative of chrysin, 5,7-bihydroxyflavone-6-sulfonate, Cu(C₁₅H₈O₇S)(3H₂O), has been prepared. The complex was characterized by elemental analysis, spectroscopic measurements and single-crystal X-ray diffraction studies. It crystallizes in the monoclinic space group C2/c, with a?=?16.036(18), b?=?6.944(8), c?=?28.03(3)?Å, β?=?94.463(17)°, V?=?3112(6)?ų, Z?=?8. In the complex, Cu(II) is five-coordinate and all donors are oxygen atoms. Hydrogen bonds and π–π stacking interactions in the crystal lead to the formation of a three-dimensional supramolecular motif.     

Synthesis,crystal and molecular structure of the copper(II) aminate complex with methionine

Russian Journal of General Chemistry - The new mononuclear complex [Cu(phen)(L-Met)H2O]Cl·2.5H2 was obtained by the reaction of the copper(II) aminate complex with L-methionine. Its structure...     

Synthesis,crystal structure and properties of a one-dimensional polymeric copper(II) complex of tetrachlorophthalate

The coordination polymer [Cu₂L₂(H₂O)₆ · 2(H₂O)] _n (L = -tetrachlorophthalate dianion) has been synthesized and characterized by X-ray crystallography, i.r. spectroscopy, electronic spectroscopy and cyclic voltammetry. The structure of the complex is a one-dimensional zigzag chain. The i.r. spectra reveal that the tetrachlorophthalate groups are bismonodentate ligands, and this is confirmed by the crystal structure determination. Cyclic voltammetry reveals two steps of a quasi-reversible oxidation–reduction processes for the complex.     

Synthesis, crystal structure and imine bond activation of a copper(II) Schiff base complex

A new copper(II) complex [Cu(HL)(ClO₄)](ClO₄) (1), where HL is a multidentate Schiff base N,N′-(2-hydroxypropane-1,3-diyl)bis(pyridine-2-aldimine), is prepared, structurally characterized by X-ray crystallography and its spectral and electrochemical properties studied. The complex forms a one-dimensional chain in the solid state structure in which the monomeric Cu(HL) units are linked by the perchlorate ligand. The complex has an axially elongated six coordinate geometry (4+2) with a CuN₄O₂ core in which the Schiff base ligand displays a tetradentate mode of bonding in the basal plane. The axial ligand is perchlorate with a significantly long Cu–O bond of ca. 2.6 Å. The one-electron paramagnetic complex displays a cyclic voltammetric response for the Cu(II)/Cu(I) couple at 0.01 V versus SCE in MeCN–0.1 M TBAP. The azomethine bond of the Schiff base in 1 on treatment with H₂O₂ undergoes oxidative conversion to form a bis(picolinato)copper(II) · dihydrate species through the formation of an amido intermediate as evidenced from the solution infrared spectral studies.     

Synthesis,characterization, crystal structure and non-isothermal dehydration kinetics of a copper(II) complex

A three-dimensional complex, [CuL₂(H₂O)]₂ (HL?=?3-hydroxy-1-adamantanecarboxylic acid), C₄₄H₆₄Cu₂O₁₄, was synthesized under hydrothermal conditions from CuCO₃?·?Cu(OH)₂ and HL. The crystal structure of the complex was determined by X-ray crystallography and its thermal behavior and IR spectra examined. The non-isothermal dehydration kinetics of the complex were investigated using the Achar differential method.     

Synthesis,crystal structure and magnetic properties of a new macrocyclic binuclear copper(II) complex

A new binuclear copper complex [CuLCl₂]₂, [L = 1-(p-tolylsulfonyl)-1,4,7- triazacyclononane], has been synthesized and structured as well as magnetically characterized. In the complex, each copper(II) atom is located in the center of a distorted square pyramidal configuration of five coordinating atoms (two nitrogen atom and three chlorine atom). Two copper(II) atoms were bridged by two chlorine anions (Cl1 and Cl1a). The distance between two copper(II) atoms is 3.483 Å. An antiferromagnetic exchange coupling effect exists in the complex.     

Synthesis,crystal structure and spectroscopic characterization of a hydrogen-bonded 1D copper(II) complex

Novel 1:2 and 1:1 (M:L) copper(II) complexes have been prepared from the tridentate ligand 2-(1-methyl-2-aza-5-oxapentyl)phenol (H₂L¹). The crystal structure of [Cu(HL¹)₂] (1) exhibits a noncentrosymmetric square-planar geometry with a slightly tetrahedral distortion. The Cu^II atom is coordinated by two amino N and two phenoxo O atoms of two (HL¹)^– ligands. The phenoxo and the alkoxy groups are involved in two strong intramolecular hydrogen bonds. The coordination moieties are further connected to a 1D linear structure by the action of intermolecular hydrogen bonds between the alkoxyl and the amino groups. The importance of steric hindrance introduced by the methyl group in the molecular structure and the packing of the complex molecules has been demonstrated. The e.p.r. parameters of (1) have been obtained: g = 2.231, g = 2.005, g _iso = 2.080, A = 185.0 G, A _iso = 86.5 G, A = (3A _iso – A )/2 = 37.3 G. These results confirm a distorted square planar stereochemistry with a ( )¹ ground state.     

Synthesis,crystal structure,and fluorescence properties of a two-dimensional copper(II) complex with Schiff base

A new Schiff base ligand C₁₉H₁₃NO₅(H₂L) was synthesized using 2-aminoterephthalic acid and 2-hydroxy-1-naphthaldehyde. A complex of this ligand [Cu(C₁₉H₁₁NO₅)(C₂H₆O)] _n was synthesized and characterized by IR, UV, fluorescence spectroscopy and X-ray diffraction single-crystal analysis. The crystal crystallizes in the monoclinic system, space group Pbca with a = 8.7745(18), b = 18.613(4), c = 24.644(5) Å, V = 4024.9(14) ų, Z = 8, F(000) = 1816, S = 1.009, ρ _calcd = 1.462 g cm^?3, μ = 1.122 mm^?1, the final R = 0.0477 and wR = 0.1594 for 4609 observed reflections (I > 2σ(I)). The Cu(II) is five-coordinated by one N atom and two O atoms from the Schiff base ligand and two carboxylate O atoms from another two ligands to form a distorted square-pyramidal geometry. Each ligand serves as a bridging ligand to link Cu²⁺ ions, leading to a two-dimensional coordination polymer. The fluorescence properties of the ligand and complex were also studied. The ligand shows strong fluorescence, and the fluorescence intensity is weakened after the Cu(II) complex formed.     

Synthesis and structure of copper(II) complex with comenic acid

Russian Journal of General Chemistry -     

Synthesis and crystal structure of divaleratobis(nicotinamide)copper(II)

A copper(II) valerate complex with nicotinamide (L) [CuL₂(C₄H₉COO)₂] (I) has been synthesized and studied by IR spectroscopy and thermogravimetry. The crystal structure has been determined. The crystals of 1 are monoclinic, a = 11.297(1) Å, b = 6.666(1) Å, c = 16.873(2) Å, b = 108.50(1)°, V = 1204.9(3) ų, Z = 2, space group P2₁/c. The structural units of the crystal of I are centrosymmetric tetragonal bipyramidal (4+2) complex molecules. The equatorial positions of the bipyramid are occupied by trans-arranged pairs of O (Cu-O, 1.973 Å) and N (Cu-N, 2.006 Å) atoms, and the axial positions are occupied by the second O atoms of the valerate anions located at longer distances (Cu-O, 2.506 Å). The supramolecular associates formed in the crystal are layers of hydrogen-bonded complexes. The disordered hydrocarbon “tails” of the valerate groups point toward the interlayer space.     

Synthesis,molecular structure and reactivity of sodium 5-sulfosalicylate dihydrate and sodium[triaqua(5-sulfosalicylato)copper(II)] 2 hemihydrate

The crystal and molecular structure of sodium 5-sulfosalicylate dihydrate, Na[(H₂Ssal)(H₂O)₂], (1) (H₃Ssal=5-sulfosalicylic acid) has been determined through X-ray diffraction analysis. The 5-sulfosalicylate anion has lost the proton at the SO₃H group but retains the usual intermolecular hydrogen bond between phenolic and carboxylic oxygen. The reaction in water of 1 with [Cu(II)(H₂O)₄]SO₄·H₂O, gives rise to the green sodium[triaqua(5-sulfosalicylato)copper(II)] 2 hemihydrate, Na[(H₂O)₃(Ssal)Cu(II)]·2×0.5H₂O, (2). The 5-sulfosalicylate anion, (Ssal³⁻), coordinates rather unusually in the syn–syn coordination mode since it binds bidentately the Cu(II) ion through the carboxylic and the phenolic oxygens, with Cu(II)O_carboxylic=1.909(4) Å and Cu(II)O_phenolic=1.885(4) Å distances. Copper(II) completes its square-planar coordination with two water molecules and in addition, perpendicularly to the square-planar coordination plane, another two water molecules with long bonds are present (Cu(II)O=2.518 and 2.912 Å). The green complex 2 reacts easily with adenine in water at pH 7 giving rise to the violet tetraadeninato(diaqua)-bis(copper(II)) dihydrate, [Cu₂(Ade)₄(H₂O)₂])]·2H₂O, (3) (Ade⁻=adeninato monoanion). This complex, that geometrically resembles copper(II) acetate monohydrate, was already described by Sletten. Finally, on the basis of the present results a possible mechanism for the anticancer activity of complex 2 and of other Cu(II)–salicylate complexes is proposed and discussed.     

Synthesis,crystal structure and magnetic properties of a new binuclear copper(II)-copper(II) complex of a macrocyclic oxamide

The binuclear metal complex [Cu(μ-exoO₂)cyclamCu(bpy)](ClO₄)₂·H₂O (bpy?=?2,2′-bipyridine and (exoO₂)cyclam?=?1,4,8,11-tetraazacyclotradecanne-2,3-dione) has been synthesized and characterized by single-crystal X-ray analysis and spectroscopic and magnetic measurements. The structure consists of homobinuclear [Cu(μ-exoO₂)cyclamCu(bpy)]²⁺ cations, a weakly coordinated water molecule and perchlorate ions. In each binuclear unit, Cu1, coordinated by four nitrogen atoms of the macrocyclic organic ligand is connected to Cu2 via the exo-cis oxygen atoms of the macrocyclic ligand with Cu···Cu separations of 5.151?Å; Cu2 assumes square-pyramidal geometry. Magnetic properties measured at 2–300?K show antiferromagnetic exchange between adjacent copper(II) ions.     

Synthesis and crystal structure of a copper(II) complex of the tridentate ligand di-(2-benzimidazolylmethyl)imine

A copper complex [Cu(IDB)Cl] · 0.5[CuCl₄]?·?H₂O (1) (IDB?=?di(2-benzimidazolylmethyl)imine) was synthesized and its structure was determined by X-ray single crystal diffraction. In this complex, the central copper(II) ion is four-coordinate, IDB serves as a neutral tridentate chelating ligand for the tetragonal copper ion. The cyclic voltammogram of complex 1 in CH₃CN gave two reversible redox waves (E _1/2,1?=??0.14?V and E _1/2,2?=?0.08?V versus SCE) which correspond to the Cu(II,?II)/Cu(I,?II) and Cu(II,?II)/Cu(II,?I) redox processes, respectively.     

Synthesis and crystal structure of dinuclear nickel (Ⅱ) complex

The crystal structure of Ni(Ⅱ) complex with 3-hydroxyl-1, 5-diazacycloheptane-N, N'-diacetate was determined by X-ray diffraction method. Crystal data for Ni2 (C9H14N2O5)2·2H2O: monoclinic, space group P21/n, a = 1.1717(5), b = 0.9794(3), c = 1.2971(2) nm, β= 96.62(3), V= 1.4786(7) nm3, Dc = 1.377 g/cm3, Z = 2,μ=13.321 cm-1 (Mo-Kα), F(000)=640. The final R and Rw are 0.075 and 0.089 respectively. The Ni(Ⅱ) ion forms 2:2 complex with ligand. Two ligands are bridged by two Ni(Ⅱ) atoms which are bridged by two O atoms. Every Ni(Ⅱ) is coordinated by two N atoms and four 0 atoms. The coordination polyhedron of the Ni(Ⅱ) ion is a distorted octahedron.     

A novel water-rich mononuclear copper(II) complex with pyridine-2,4-dicarboxylate: Synthesis and crystal structure

A new monomolecular copper(II) complex, [Cu(Phen)₂(Pda)] · 9H₂O (I) (H₂Pda = pyridine-2,4-dicarboxylate acid, Phen = 1,10-phenanthroline), has been prepared from H₂Pda and Phen at room temperature and characterized by IR, elemental analysis, X-ray powder diffraction, and single-crystal X-ray diffraction. Structure analysis shows that each Cu(II) is coordinated by two Phen ligands and one Pda ligand to complete a octahedron CuN₅O chromophore. In addition, a unique water networks paralleling to (001) composed by the crystallization water through hydrogen bonds play a important role in the stability of crystal structure. The crystal structure is found to be orthorombic with space group Pbcn and cell parameters a = 13.651(4), b = 22.516(7), c = 22.386(7) Å, R ₁ = 0.0735 and wR ₂ = 0. 0.1935.