Synthesis and study of lead(II) uranate Pb(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>O<Subscript>2</Subscript>(OH)<Subscript>2</Subscript>·H<Subscript>2</Subscript>O

An individual crystalline compound Pb(UO₂)₂O₂(OH)₂·(H₂O) was obtained by reaction of synthetic schoepite UO₃·2.25H₂O with an aqueous solution of lead(II) nitrate under hydrothermal conditions. The composition and structure of this compound were determined, and the processes of its dehydration and thermal decomposition were studied by chemical analysis, X-ray diffraction, IR spectroscopy, and thermography.     

Geometric and electronic structure of an N,N′-ethylene-bis(salicylaldiminato) zinc(II) molecule,ZnO<Subscript>2</Subscript>N<Subscript>2</Subscript>C<Subscript>16</Subscript>H<Subscript>14</Subscript>

Gas electron diffraction at a temperature T of 641(5) K is used to study the structure of an N,N′-ethylenebis(salicylaldiminato) zinc(II) molecule, ZnO₂N₂C₁₆H₁₄, further Zn(salen). The structure of a gaseous Zn(salen) complex has C ₂ symmetry and is characterized by a substantial turn of two chelating fragments of the ligand with respect to each other, and also by a big difference in the length of coordination bonds: r _h1(Zn-O)=1.902(7) Å r _h1(Zn-N)= 2.027(7) Å. Results of the DFT/B3LYP calculation with 6-31G* and CEP,TZV basis sets of the molecule structure well agree with the experimental data. The electronic structure of Ni(salen), Cu(salen), Zn(salen), and Zn(acacen) molecules is considered.     

Hydrothermal synthesis and crystal structure of a novel nickel(II) complex: [Ni(H<Subscript>2</Subscript>Bibzim)<Subscript>3</Subscript>Cl<Subscript>2</Subscript> · 2H<Subscript>2</Subscript>O] (H<Subscript>2</Subscript>Bibzim = 2,2-Bibenzimidazole)

A novel organic-inorganic hybrid compound based on weak intermolecular interactions formulated as Ni(H₂Bibzim)₃Cl₂ · 2H₂O (H₂Bibzim = 2,2-bibenzimidazole, formula, C₁₄H₁₀N₄) has been synthesized under hydrothermal conditions and characterized by elemental analysis, single-crystal X-ray diffraction analyses, and IR spectra. It crystallizes in the orthorhombic system, space group Pbcn, Z = 2, a = 20.8530(19), b = 15.7838(14), c = 12.3159(11) Å, V = 4053.7(6) ų, M _r = 1736.84, ρ_c = 1.423g/cm³, λ = 0.71073 Å, μ(MoK _α) = 0.664 mm^?1, F(000) = 1792, R = 0.0283 and wR = 0.0707 for 3746 observed reflections with I > 2σ(I). The complex is composed of mononuclear cations [Ni(H₂Bibzim)₃]²⁺, chlorine anions, and lattice water molecules, which are linked into a two-dimensional supramolecular architectures via hydrogen bonds and π-π-stacking interactions.     

Synthesis,IR-spectroscopic study and crystal structure of tris(benzohydrazide)nickel(II) dichloride dihydrate [Ni(L)<Subscript>3</Subscript>]Cl<Subscript>2</Subscript> · 2H<Subscript>2</Subscript>O

Coordination compound [Ni(L)₃]Cl₂ · 2H₂O (L is benzohydrazide) has been synthesized and studied by IR spectroscopy and X-ray diffraction analysis. According to X-ray diffraction, one of the Cl^– ions is disordered over two nonequivalent positions. The crystals are monoclinic, a = 15.423(3) Å, b = 9.697(2) Å, c = 18.893(4) Å, ß = 105.99(3)°, space group P2₁/c, Z = 4. The structural units of the crystal are complex cations [Ni(L)3]2+, in which ligands L are coordinated to the central atom bidentately chelating the metal atoms through the O and N atoms of the hydrazide moiety (Ni–O 2.036(4), 2.051(5), 2.047(5); Ni–N 2.095(5), 2.089(6), 2.097(6) Å). The structural units of the crystal are joined together by cation–anion electrostatic interactions and hydrogen bonds, which involve both H₂O molecules, both Cl^– anions and the N atoms of chelate rings of the complex cation.     

Synthesis of 14H-dibenzo xanthene derivatives using choline chloride/tin(II) chloride deep eutectic solvent and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/ƛ-carrageenan/Zn(II)

In this study, various xanthene derivatives have prepared efficiently through a simple method using choline chloride/tin(II) chloride (ChCl·2SnCl₂) deep eutectic solvent (DES), alone, or in the presence of Fe₃O₄/?-carrageenan/Zn(II) magnetic bionanocatalyst. In the employed procedure, 2-naphthol derivatives have mixed with aromatic or aliphatic aldehydes and the reactions have been completed in the presence of DES at 90 °C in 1.5 h. In addition, using DES/Fe₃O₄/?-carrageenan/Zn(II), the reaction time was reduced to 30 min. The employed DES has been recycled four times without important loss of its activity.     

Crystal structures of chiral (R/S) (C<Subscript>8</Subscript>H<Subscript>11</Subscript>N)<Subscript>2</Subscript> · Zn(OAc)<Subscript>2</Subscript>

Two opposite configuration (R/S) of chiral complexes (C₈H₁₁N)₂ · Zn(OAc)₂ (Ia and Ib—L-(−)-) and D-(+)-isomer) were synthesized by a simple one-pot method. The crystal structures of Ia and ib determined by X-ray crystallography.     

Synthesis,characterization, spectroscopic,and thermal studies of imidazole complexes of metal benzenesulfonates. Crystal structure of [M(imH)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>]·(BS)<Subscript>2</Subscript> [M=Ni(II) and Co(II)]

Four novel transition metal benzenesulfonate (BS) complexes of imidazole (im) with a general formula [M(imH)₃(H₂O)₃]·(BS)₂ [M=Mn(II) (1), Ni(II) (2), Co(II) (3)] and [Cu(BS)(imH)₃]·(BS) (4) have been synthesized and characterized by physicochemical and spectroscopic methods. The complexes 2 and 3 have also been characterized by single X-ray diffraction technique. The BS anion in complexes 1–3 acts as a counter anion, while in complex 4, it acts as both ligand and counter anion. The Ni and Co complexes are isomorphous, crystallizing in the monoclinic crystal system with C2/c space group. Each metal(II) atom in 2 and 3 is octahedrally coordinated by three imidazole and three aqua ligands, adopting a mer-coordination mode with Ni(II) or Co(II) centers. In both 2 and 3, the H2C atom has bifurcated donor (O3 and O5) atoms, forming a bifurcated hydrogen bond. This hydrogen bond links the complex cation and BS anion, forming one-dimensional hydrogen-bonded supramolecular chains. The complexes exhibit different decomposition characteristics. Magnetic susceptibility measurement shows that complex 3 has orbital interactions.     

Copper(II) oxalate obtained through the reaction of 1,2-ethanediol with Cu(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>·3H<Subscript>2</Subscript>O

The paper presents the experimental results of the structural investigations and thermal analysis of copper(II) oxalate, a polynuclear coordination compound, obtained by a new method, through the reaction of 1,2-ethanediol with Cu(NO₃)₂·3H₂O. The reaction between 1,2-ethanediol and Cu(NO₃)₂·3H₂O occurs, under some working conditions, with the oxidation of 1,2-ethanediol to the oxalate anion (L). The synthesized polynuclear coordination compound, [CuL·0.3H₂O]_n, was characterized by chemical analysis, electronic and vibrational spectra and thermal analysis. The thermal properties of the polynuclear coordination compound have been investigated by TG, DTG and DSC. The obtained decomposition product is CuO. Powder XRD (X-ray diffraction), IR spectroscopy and TEM (transmission electron microscopy) were used to characterize the composition, the crystalline structure and the surface morphology of the copper oxide obtained through thermolysis. The thermal conversion product, copper(II) oxide, has a microporous structure with a large specific area.     

Synthesis and crystal structure of two {M(4,4′-dpdo)<Subscript>2</Subscript>[N(CN)<Subscript>2</Subscript>]<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>} complexes (M = Co(II), Mn(II); 4,4′-dpdo = 4,4′-bipyridyl-N,N′-dioxide)

The ligand 4,4′-bipyridyl-N,N′-dioxide (4,4′-dpdo) was used in the synthesis of two complexes, {Co(4,4′-dpdo)₂[N(CN)₂]₂(H₂O)₂} (1) and {Mn(4,4′-dpdo)₂[N(CN)₂]₂(H₂O)₂} (2). The complexes were found to be isostructural, triclinic, space group P-1 with Z = 1 and the following unit cell parameters: a = 8.158(8) Å, b = 8.865(8) Å, c = 9.477(9) Å; α = 70.988(13)°, β = 78.778(13)°, γ = 71.964(10)°; V = 612.8(10) ų for 1; a = 8.247(14) Å, b = 9.001(16) Å, c = 9.707(17) Å; α = 71.02(2)°, β = 78.63(2)°, γ = 72.62(2)°; V = 646(2) ų for 2. Final R-values were 0.075 and 0.083 for 1 and 2, respectively. In the molecules of the complexes, Co(II) or Mn(II) cation is coordinated by two O-atoms of two 4,4′-dpdo ligands, two terminal N-atoms of two dicyanamides, and two O-atoms of water molecules. The crystals are molecular, with adjacent complex molecules linked through a system of O-H...N and O-H...O hydrogen bonds.     

Monodentate coordinated chromate(VI) ion in [Cu(phen)<Subscript>2</Subscript>OCrO<Subscript>3</Subscript>](phen)<Subscript>0.5</Subscript>·4H<Subscript>2</Subscript>O completing the square pyramidal geometry of the copper(II) in the solid state

Novel copper(II) complex of the formula [Cu(phen)₂OCrO₃](phen)_0.5 ·4H₂O (1) (phen = 1,10-phenantroline) was prepared in the crystalline form and characterized by X-ray diffraction and spectroscopic methods (IR-FIR, NIR-Vis–UV, EPR). In the solid state, the CuN₄O chromophore adopts a slightly distorted square-pyramidal geometry around the Cu²⁺ ion with a magnitude of a distortion parameter τ = 0.14. The chromate unit in (1) was found to be a monodentate.     

Nickel(II) and Iron(II) coordination compounds with octahydrotriborate(1–) anion [ML<Subscript>3</Subscript>]{B<Subscript>3</Subscript>H<Subscript>8</Subscript>}<Subscript>2</Subscript> (M = Fe<Superscript>2+</Superscript>, Ni<Superscript>2+</Superscript>; L = bipy,phen)

Methods of synthesis have been developed for new types of promising precursors of metal borides, coordination compounds [ML₃]B{₃H₈{₂ (M = Fe²⁺, Ni²⁺; L = bipy, phen), using modified procedures of synthesis of octahydrotriborate anion. Compounds [Ni(bipy)₃]B{₃H₈}₂, [Ni (phen)₃]B{₃H₈}₂ and [Fe(phen)₃]B{₃H₈}₂ were prepared and characterized by single-crystal X-ray diffraction.     

Novel copper(II) complex with unusual π-stacking structure, [Cu(SSC)Cl]<Subscript>2</Subscript>·CH<Subscript>3</Subscript>OH·2H<Subscript>2</Subscript>O (SSC = salicylaldehyde semicarbazone anion)

The crystal structure of [Cu^II(SSC)Cl]₂·CH₃OH·2H₂O (SSC = salicylaldehyde semicarbazone anion) was determined by the single crystal X-ray diffraction method at 293 K. Crystal data for Cu₂C₁₇H₂₄Cl₂N₆O₇: a = 10.272(2) Å, b = 10.297(2) Å, c = 11.462(2) Å, α = 82.860(3)°, β = 78.384(3)°, γ = 81.330(2)°, triclinic, space group P1¯, Z = 2, d _calc = 1.769 g/cm³, R ₁ = 0.038. One N and two O atoms of SSC^? occupy three coordination sites around Cu(II). The fourth site is occupied by Cl^? to yield distorted square-planar environment. Two molecules of the complex form a planar dimer through intermolecular N-H?O hydrogen bonds. The most striking feature of the crystal structure is the packing of the planar dimers within the crystal. The interplanar distances between adjacent two layers are 3.280 Å, indicative of strong π-π noncovalent interactions. The methanol solvent and water molecules are included as additional components in the crystal.     

Synthesis of solvates of the copper(II) complex with chiral caryophyllane-type morpholino oxime (HL). Structure of Cu(HL)Cl<Subscript>2</Subscript> · CHCl<Subscript>3</Subscript>

Paramagnetic Cu(HL)Cl₂ · 0.25CHCl₃ (I) and Cu(HL)C1₂ · 0.25CH₂C1₂ (II), where HL is the optically active morpholino oxime obtained from the terpenoid caryophyllene, were synthesized. The crystals of Cu(HL)Cl₂ · CHCl₃ (III) were isolated. According to X-ray diffraction data, the crystals of III are composed of acentric mononuclear complex molecules Cu(HL)Cl₂ and solvate molecules CHCl₃. In the complex molecules, the Cu ion coordinates two N atoms of the bidentate chelating ligand HL and two C1 atoms at the vertices of a distorted tetrahedron. The translationally identical molecules of the complex combined by H-bonds form chains along the axis x.     

Crystal structure of a novel binuclear Cu(II) complex Cu<Subscript>2</Subscript>[(Dmbiim)<Subscript>4</Subscript>H<Subscript>2</Subscript>O](ClO<Subscript>4</Subscript>)<Subscript>4</Subscript>·3H<Subscript>2</Subscript>O

A novel complex, Cu₂[(Dmbiim)₄H₂O](ClO₄)₄·₃H₂O (Dmbiim = 1.1′-dimethyl-2.2′-biimida-zole), has been synthesized and studied by X-ray crystallography. Crystal data for CuO₉N₈C₁₆Cl₂H₂₂: a = 10.160(2) Å, b = 12.991(3) Å, c = 20.646(4) Å, β = 101.443(3)°, space group P2(1)/c, Z = 4, d _calc = 1.504 g/cm³, R = 0.0718. The crystal structure reveals that the complex is cage-shaped, with two Cu ions bridged by Dmbiim and each Cu ion chelated by the oxygen atom of water and four nitrogen atoms of Dmbiim.     

Synthesis,crystal structure and magnetic properties of a novel manganese(II)-nitronyl nitroxide-azido(μ<Subscript>1,1</Subscript> and μ<Subscript>1,3</Subscript>) one-dimensional complex

A novel one-dimensional manganese(II) complex containing nitronyl nitroxide radical [Mn₂(IM2-py)₂(Ac)₂(μ_1,1-N₃)(μ_1,3-N₃) · EtOH] _n was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group p2₁/n. Each Mn(II) ion is six-coordinated in a distorted octahedral environment. The two N atoms of the nitronyl nitroxide radical and the two O atoms of acetate ligands are in the equatorial plane, whereas the two different azido bridging ligands are in trans axial position. Mn(II) ions are linked by nitrogen atom of μ_1,1-azido and oxygen atoms of two carboxy groups to form a Mn-Mn unit. Mn-Mn units are linked by azido ligands through μ_1,3 bridging style to form a one-dimensional chain. The compound is connected by the coordination bonds, π-π interactions and hydrogen bonds as a three-dimensional structure. Magnetic susceptibility data support that there are stronger antiferromagnetic interactions between the radical and Mn(II) ion, weak antiferromagnetic interactions between the Mn-R units, and very weak antiferromagnetic interactions between the R-Mn-Mn-R units.     

Synthesis and structural characterization of a novel tetranuclear Cu(II) complex: [Cu<Subscript>4</Subscript>L<Subscript>2</Subscript>(pic)<Subscript>4</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>]·2H<Subscript>2</Subscript>O

A novel Salen-type bisoxime ligand, 6,6′-dimethoxy-2,2′-[(1,4-butylene)dioxybis(nitrilomethylidyne)]diphenol (H₂L) and its tetranuclear Cu(II) complex, [Cu₄L₂(pic)₄(H₂O)₂]·2H₂O, have been synthesized and characterized by elemental analyses, IR, TG-DTA and ¹H-NMR etc. The X-ray crystal structure of the complex reveals that formation of a tetranuclear structure, which consists of four copper(II) atoms, two pentadentate L²⁻units, four picratols, two coordinated water molecules and two crystallizing water molecules. Around four copper ions are all octahedral geometries. It was demonstrated that the picratols in the tetranuclear copper(II) complex show a novel tridentate coordination mode.     

Crystal structure of the ruthenium(II) nitrosotrichloro complex Na[RuNOCl<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)OH]·2H<Subscript>2</Subscript>O

The crystal structure of the coordination compound Na[RuNOCl₃(H₂O)OH]·2H₂O is reported. The complex is studied by IR and NMR spectroscopy, powder and single crystal X-ray diffraction. Crystallographic data determined for H₇Cl₃NNaO₅Ru is: a = 6.648(2) ?, b = 8.216(7) ?, c = 10.063(3)?, α= 89.75(6)°, β = 70.96(2)°, γ = 78.76(5)°, V = 967.9(2) ?³, P1 space group, Z = 4, d _x = 2.165 g/cm³.     

Two novel sandwich copper(II) complexes [CuLCl]<Subscript>2</Subscript>[CuCL<Subscript>4</Subscript>] and [CuLBr]<Subscript>2</Subscript>[CuBr<Subscript>4</Subscript>] (L = N,N′-bis(furaldehyde)diethylenetriamine)

The novel trinuclear copper(II) complexes [CuLCl]₂[CuCl₄](I) and [CuLBr]₂[CuBr₄] (II) (where L = N,N′-bis(furaldehyde) diethylenetriamine) were synthesized and structurally characterized by X-ray diffraction. They consist of sandwich units. Both I and II crystallize isomorphously in the monoclinic space group P2/n and feature cation/anion/cation geometry. The novel trinuclear copper(II) complexes I and II shown to be stabilized by a number of weak hydrogen bonds and intermolecular π-π stacking interactions. The article is published in the original.     

Erbium(III) and lutecium(III) complexes [Ln(H<Subscript>2</Subscript>O)<Subscript>8</Subscript>][Cr(NCS)<Subscript>6</Subscript>] · 5H<Subscript>2</Subscript>O: Synthesis and crystal structure

[Ln(H₂O)₈][Cr(NCS)₆] · 5H₂O aqua complexes, where Ln = Er (1), Lu (2), have been found in an aqueous solution instead of binary complex salts with an organic ligand in their cation, when crystal products of the reaction between Ln(NO₃)₃ · 6H₂O (Ln = Er, Lu), K₃[Cr(NCS)₆] · 4H₂O, and 8-oxyquinoline (C₉H₇NO) were studied by X-ray diffraction. Crystals of complexes 1 and 2 are isostructural and crystallize in triclinic system, space group P\(\bar 1\), Z = 2. For complex 1: a = 9.0677(4) Å, b = 9.3115(4) Å, c = 16.9595 Å, α = 81.526(2)°, β = 86.153(2)°, γ = 83.879(2)°, V = 1406.33(10) ų, ρ_calc = 1.894 g/cm³; for complex 2: a = 9.0438(3) Å, b = 9.2880(3) Å, c = 16.9181(3) Å, α = 81.7250(10)°, β = 86.1600(10)°, γ = 83.8850(10)°, V = 1396.38(7) ų, ρ_calc = 1.926 g/cm³.     

Interaction of hydantoins with transition metal ions: synthesis,structural, spectroscopic,thermal and magnetic properties of [M(H<Subscript>2</Subscript>O)<Subscript>4</Subscript>(phenytoinate)<Subscript>2</Subscript>] M = Ni(II), Co(II)

Complexes of Ni(II) and Co(II) of the formulae [Ni(H₂O)₄(pht)₂] (1) and [Co(H₂O)₄(pht)₂]·1,5NH₃·H₂O (2) (where pht = phenotoinate anion) were obtained and characterized physicochemically. [Ni(H₂O)₄(pht)₂] (1) crystallizes in a monoclinic space group P2₁/c; a = 11.7358(8), b = 11,1250(8), 11.4182(7) Å; β = 97.076(5)°; V = 1479.41 Å³; Z = 2. The environment around the nickel and cobalt ions can be described as a distorted octahedron. The metal ion was found to bind to four water molecules and two nitrogen atoms derived from two anions of the monodentate phenytoinate. Four intramolecular hydrogen bonds designated as S(6) graph set are found in one [Ni(H₂O)₄(pht)₂] (1) molecule. Two chain HB patterns, constructed by the [Ni(H₂O)₄(pht)₂] molecules extending along the c and b axes, respectively, have been observed. The cobalt complex precipitates with the additional solvent molecules: one and a half of ammonia and one water. The results document the preferential binding of hydantoins to the metal ions through N(3) atom.