Stability of gold(I) glycinate complexes in aqueous solution

The stepwise substitution equilibrium AuCl ₂ ^? +iX^?=AuCl_2?i X _i ^? +iCl^?, β_i, where X^? is the glycinate ion (H₂N-CH₂-COO^?), i = 1 or 2, at 25°C in an aqueous solution with I = 1.0 mol/L (NaCl) has been studied pH-metrically. The corresponding constants are logβ₁ = 3.60 ± 0.10, and logβ₂ = 6.2 ± 0.2.     

Nongeneral Character of the Resonance Parameters Σ<Stack><Subscript>R</Subscript><Superscript>+</Superscript></Stack> of Silicon-, Germanium-, and Tin-Containing Substituents in Radical Cations

The resonance parameters σ _R ⁺ of substituents Y in radical cations YD^+· [where D is a π- or n-type center, and Y = MMe₃, CH₂MMe₃ (M = Si, Ge, Sn), C(SiMe₃)₃] depend on the nature of both Y and D. Using radical cations YD^+· (Y = CH₂SiMe₃, SnMe₃) as examples, it was found that the two conjugation parameters, constants σ _R ⁺ of substituents Y and perturbation energy calculated by the modified molecular orbital perturbation method, are linearly related to each other. The energies of donor and acceptor components of the overall resonance effect of CH₂SiMe₃ and SnMe₃ with respect to radical cation centers D^+· were estimated for the first time. The donor energy constituent in YD^+· is considerably greater than in neutral DY molecules.     

Stability of diammine and chloroammine gold(I) complexes in aqueous solution

The substitution equilibria AuCl ₂ ^? + iNH ₄ ⁺ = Au(NH₃)_iCl_{2 ? i} + iCl^? + iH⁺, β _i ^* . were studied pH-metrically at 25°C and I = 1 mol/L (NaCl) in aqueous solution. It was found that logβ ₁ ^* = ?5.10±0.15 and logβ ₂ ^* = ?10.25±0.10. For equilibrium AuNH₃Cl_solid = AuNH₃Cl, log K _s = ?3.1±0.3. Taking into account the protonation constants of ammonia (log K _H = 9.40), the obtained results show that for equilibria AuCl ₂ ^? + iNH₃ = Au(NH₃)_iCl_{2 ? i} + iCl^?, logβ₁ = 4.3±0.2, and logβ₂ = 8.55±0.15. The standard potentials E ₀ ^1/0 of AuNH₃Cl⁰ and Au(NH₃) ₂ ⁺ species are equal to 0.90±0.02 and 0.64±0.01 V, respectively.     

Theoretical study of stepwise chlorinated aluminide clusters Al<Subscript>13</Subscript>Cl<Stack><Subscript><Emphasis Type="Italic">n</Emphasis></Subscript><Superscript>−</Superscript></Stack> (<Emphasis Type="Italic">n</Emphasis> = 1–9)

The electronic and geometric structures, energy stabilities, normal mode frequencies, and spin density distributions (in radicals) of different stepwise-chlorinated aluminum clusters Al₁₃Cl _n ^? (n = 1–9) are calculated within the B3LYP approximation of the density functional theory using 6-31G* and 6-311+G* basis sets. The results are compared with analogous computation data on hydrides Al₁₃H _n ^? (n = 1–12) obtained at the same level. The general qualitative pattern for related series of hydrides, chlorides, and iodides (as well as fluorides and bromides) turns out to be similar in many respects. For all Al₁₃X _n ^? clusters with different electronegative substituents X, there is a set of a considerable number of low-lying closely spaced inner isomers (with a centered icosahedral cage), marquee isomers, and outer isomers (capped). The effects found by calculations in centered icosahedral isomers—localization of spin density on the trans-Al* atom in radical anions and its associated trans addition rule for an even substituent and the zigzag (odd-even) dependence of the energies D _n (X) of successive addition of substituents X to the metal cage on n described in the framework of the molecular model of the valence states of the Al ₁₃ ^? superatom—should also be shared by many Al₁₃X _n ^? series with different X’s. The differences between hydrides Al₁₃H _n ^? and chlorides Al₁₃Cl _n ^? of the same type are quantitative. For the hydrides, inner isomers are preferable in the first half of the series (n = 1–6); and in the second half (n = 7–12), outer isomers are more favorable. For the chlorides, icosahedral isomers are preferable only at the very beginning of the series. In the other cases, nonicosahedral structures are most favorable, for which the situation becomes very complicated due to the large number of position isomers and the aforementioned simple rules found for centered icosahedral structures are fulfilled to a considerably less extent or not at all.     

Radiation polymerization of methacrylates controlled by a chain transfer catalyst

The effect of γ-radiation dose and chain transfer catalyst on polymerization of methyl methacrylate (MMA) and copolymerization of MMA with hydroxyethyl methacrylate or triethylene glycol dimethacrylate has been investigated. The addition of 5 × 10^?4?10^?3 mol/L of bis[(difluoroboryl) isopropylpyridine dimethylglyoximato]cobalt(II) (Co(II)) makes it possible to produce macromonomers MM _n ⁼⁼ bearing terminal double bonds and having a degree polymerization of n = 2?40 and a polydispersity index of 1.05?1.15. It has been found that the degree polymerization of the macromonomers increases with the increasing γ-radiation dose and monomer conversion through the mechanism of the reversible β-cleavage of the terminal unit: R _k ^? + MM _n ⁼ ? MM _k+1 ⁼ + R _n-1 ^? followed by the living polymerization of both radicals. This reaction may compete with the catalytic chain transfer reaction and have a significant effect on the evolution of the molecular weight characteristics of the macromonomers during the course of MMA (co)polymerization.     

4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]-hexacosane Bis(nitrate-hydrogennitrate): Synthesis and crystal structure

A crystalline adduct of 2.2.2-cryptand and nitric acid, [H₂(Crypt-222)]²⁺·2(NO ₃ ^? ·HNO₃) (I), is synthesized and studied using X-ray diffraction analysis. The monoclinic structure of compound I (space group C2/c, a = 13.326 Å, b = 15.262 Å, c = 15.020 Å, β = 98.96°, Z = 4) is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.067 for 2647 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). In the structure of compound I, the 2.2.2-cryptand dication lies on an axis 2 and has an endo-endo conformation, for which two H atoms at two protonated N atoms are directed inside the cavity. One of the NO ₃ ^? ·HNO₃ dimers is situated in the inversion center, and the other dimer lies on another axis 2 and is disordered over three orientations. All H atoms in the NO ₃ ^? ·HNO₃ dimers are equiprobably disordered over two close sites. Each of the two NO ₃ ^? ·HNO₃ dimers is formed by the very strong disordered N-O-H···O=N hydrogen bond between the nitric acid molecule and nitrate anion.     

Hydrogen bonded С–H···Y (Y = O,S, Hal) molecular complexes: A natural bond orbital analysis

Hydrogen bonded C–H···Y complexes formed by H₂O, H₂S molecules, hydrogen halides, and halogen-ions with methane, halogen substituted methane as well as with the C₂H₂ and NCH molecules were studied at the MP2/aug-cc-pVDZ level. The structure of NBOs corresponding to lone pair of acceptor Y, n_Y, and vacant anti-σ-bond C–H of proton donor was analyzed and estimates of second order perturbation energy Е⁽²⁾ characterizing donor–acceptor n_Y → σ_C-H^* charge-transfer interaction were obtained. Computational results for complexes of methane and its halogen substituted derivatives show that for each set of analogous structures, the Е_nY→σ*C-H⁽²⁾ energy tends to grow with an increase in the s-component percentage in the lone pair NBO of acceptor Y. Calculations for different C···Y distances show that the equilibrium geometries of complexes lie in the region where the E⁽²⁾ energy is highest and it changes symbatically with the length of the covalent С–H bond when the R(C···Y) distance is varied. The performed analysis allows us to divide the hydrogen bonded complexes into two groups, depending on the pattern of overlapping for NBOs of the hydrogen bridge.     

Field-induced π-polarization in barrelene derivatives: a computational study based on structural variation

Barrelene, H–C(CH=CH)₃C–H, is an unsaturated polycyclic hydrocarbon containing three isolated double bonds in a non-planar arrangement. We have studied the transmission of field effects through the barrelene framework by analyzing the small structural changes occurring in the phenyl group of many Ph–C(CH=CH)₃C–X molecules, where X is a variable substituent. Molecular geometries have been determined by quantum chemical calculations at the HF/6-31G* and B3LYP/6-311++G** levels of theory. Comparison with the results obtained for the corresponding saturated molecules, the bicyclo[2.2.2]octane derivatives Ph–C(CH₂–CH₂)₃C–X, reveals a small, but significant, field-induced π-polarization of the barrelene cage, especially when the remote substituent is a charged group. Additional evidence of π-polarization is obtained by comparing the electric dipole moments of the two sets of uncharged molecules. The structural variation of the barrelene cage caused by the variable substituent in Ph–C(CH=CH)₃C–X molecules has also been investigated. It is much larger than that of the phenyl group and depends primarily on the electronegativity of the substituent. Particularly pronounced is the concerted variation of the non-bonded distance between the bridgehead carbons of the cage, r(C···C) ₁ ^BARR , and the average of the three C–C–C angles at the cage carbon bonded to the variable substituent, α ₁ ^BARR . A scattergram of r(C···C) ₁ ^BARR versus the corresponding parameter for bicyclo[2.2.2]octane derivatives, r(C···C) ₁ ^BCO , shows that the variation of r(C···C) ₁ ^BARR becomes gradually less pronounced than that of r(C···C) ₁ ^BCO as the electronegativity of the substituent increases.     

The thermodynamic characteristics of vaporization in the NaI-PrI<Subscript>3</Subscript> system

The vaporization of the NaI-PrI₃ quasi-binary system was studied by high-temperature mass spectrometry over the whole concentration range. At 623–994 K, saturated vapor contained not only (NaI) _n and (PrI₃) _n molecules (n = 1, 2) and Na⁺(NaI) _n (n = 0–4) and I^?(PrI₃) _n (n = 1–2) ions but also mixed molecular and ionic associates recorded for the first time (NaPrI₄, Na₂PrI₅, NaPrI ₃ ⁺ , Na₂PrI ₄ ⁺ , Na₃PrI ₅ ⁺ , Na₄PrI ₆ ⁺ , NaPrI ₅ ^? , and NaPr₂I ₈ ^? ). The partial vapor pressures of molecules were calculated, and the equilibrium constants of the dissociation of neutral and charged associates were measured. The enthalpies of molecular and ion-molecular reactions were determined, and the enthalpies of formation of gaseous molecules and ions were obtained.     

Synthesis and crystal structure of hexa(nitrato-<Emphasis Type="Italic">O,O</Emphasis>′)dysprosium(III) Bis[4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane] nitrate dihydrate

A new complex salt 2[H₂(Crypt-222)]²⁺ · [Dy(NO₃)₆]^3? · NO ₃ ^? · 2H₂O is synthesized, and its crystal structure is studied by X-ray diffraction analysis (space group R \(\bar 3\), a = 11.445 Å, c = 38.981 Å, Z = 3; direct method, full-matrix least-squares method in the anisotropic approximation, R = 0.027 for 3555 independent reflections; CAD4 automated diffractometer, λMoK _α radiation). The [Dy(NO₃)₆]^3? anion and 2.2.2-cryptand dication lie on axis \(\bar 3\). The [Dy(NO₃)₆]^3? ligand in the [Dy(NO₃)₆]^3? anion is disordered. The Dy³⁺ cation has slightly distorted octahedral coordination with all six split vertices at the O atoms of the six symmetrically equivalent disordered NO ₃ ^? ligands.     

Theoretical study of oxoborate complexes with MO<Stack><Subscript>4</Subscript><Superscript><Emphasis Type="Italic">n</Emphasis>−</Superscript></Stack> tetraoxo anions in the inner and outer spheres of the B<Subscript>20</Subscript>O<Subscript>30</Subscript> cluster

The energies and structural and spectroscopic characteristics of endohedral (MO₄©B₂₀O ₃₀ ^n? ) and exohedral (MO₄ · B₂₀O ₃₀ ^n? ) isomers of oxoborate complexes with MO ₄ ^n? tetraoxo anions with 32 valence electrons located in the inner and outer spheres of the B₂₀O₃₀ cluster have been calculated by the density functional theory method (B3LYP). It has been demonstrated that, among the endohedral MO₄©B₂₀O ₃₀ ^n? clusters with strong multiply charged anions (VO ₄ ^3? , CrO ₄ ^2? , PO ₄ ^3? , SO ₄ ^2? , AsO ₄ ^3? , SeO ₄ ^2? , etc.), the isomer in which a “guest” tetrahedron MO₄ is located at the center of the B₂₀O₃₀ cage and bonded to it through internal oxygen bridges M-O*-B is the most favorable one. Among the exohedral analogues MO₄ · B₂₀O ₃₀ ^n? , two most favorable isomers contain the “capping” MO₄ tetrahedron bonded to the B₂₀O₃₀ cage through two and three external M-O-B bridges. For the complexes with doubly charged SO ₄ ^2? and SeO ₄ ^2? anions, the third exohedral isomer in which the sulfite or selenite group MO₃ is bidentately coordinated to the oxidized B₂₀O₂₉(OO) cage with one peroxide bridge turns out to be close in energy to the above two isomers. For the systems with high negative charge n, the exohedral isomers are much more favorable than the endohedral isomer; however, with decreasing charge, the difference in energy between them decreases to ~10–18 kcal/mol, so that the exo–endo transition between them can require moderate energy inputs. For the endohedral complexes with singly charged ClO ₄ ^? and BrO ₄ ^? anions, two isomers with close energies are preferable in which the central atoms of the guest tetrahedra are reduced to the state of singly charged ions, while the oxoborate cage is oxidized to B₂₀O₂₆(OO)₄ with four peroxide groups B-O-O-B and retains its closed (closo) structure. In the most favorable isomer of the complexes with multicharged ortho-anions BO ₄ ^5? , CO ₄ ^4? , and NO ₄ ^3? , the outersphere anion is reduced to, respectively, borate, carbonate, and nitrate bidentately coordinated to the oxidized B₂₀O₂₉(O)₂ cage with an open structure and two strongly elongated terminal B-O bonds. The results are compared with the data of previous calculations of endohedral and exohedral vanadate complexes MO₄©V₂₀O ₅₀ ^n? and MO₄ · V₂₀O ₅₀ ^n? with the same guest anions MO ₄ ^n? .     

Electronic Structure and Relative Stabilities of 10- and 12-Vertex. <Emphasis Type="Italic">Closo</Emphasis>and <Emphasis Type="Italic">Nido</Emphasis>-Heteroborane Clusters of Ga,Ge, and As Elements

A DFT method with the B3LYP functional and the 6-311++G(d,p) diffuse basis set is used to predict geometries, relative stabilities, electronic structures, and the bonding of closo- and nido-Ga_mB_n–mH _n ^2? , Ge_mB_n–mH _n ^m?2 , and As_mB_n–mH _n ^{2 m?2} (n = 10, 12 and m = 1, 2) Clusters are obtained by replacing BH with isolobal GaH, GeH⁺, and AsH²⁺ fragments, keeping the same skeleton electron pairs (SEP). Based on the polyhedral skeletal electron pairs theory (PSEPT), closo and nido structures are predicted and can be of significant interest for experimentalists working in the field of heteroboranes. Different cluster stabilities are studied according to Gimarc′s and Williams′ rules, where our calculations show that the monosubstituted clusters deviate from these rules, giving rise to open structures. As₂B₈H _n ²⁺ as 10-vertex structures lead to nido-type clusters, however, Ge_mB_n–mH _n ^m?2 (n = 10, 12 and m = 1, 2) give rise to closo isomers with close energies. All optimized structures exhibit large HOMO–LUMO gaps suggesting a good kinetic stability, thus predicting their isolation and characterization.     

Crystal structure of 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo [8.8.8]hexacosane nitrate-hydrogen nitrate perchlorate semihydrate

An adduct of 2.2.2-cryptand with nitric and perchloric acids of the [H₂(Crypt-222)· 0.52H₂O]²⁺·ClO ₄ ^? ·NO ₃ ^? ·HNO₃ composition (I) is prepared and characterized by single crystal X-ray diffraction. The triclinic structure of I (space group \(P\overline 1 \), a = 10.176 Å, b = 11.272 Å, c = 12.870 Å, α = 78.61°, β = 76.62°, γ = 79.88°, Z = 2) is solved by a direct method and refined in the full-matrix anisotropic approximation to R = 0.062 for all 3642 measured independent reflections (CAD-4 automated diffractometer, λMoK _α). The structure of I contains a dication of 2.2.2-cryptand in the endo-endo conformation, two hydrogen atoms at the protonated N atoms are directed inside the cavity which also includes a water molecule with a site occupation factor of 0.52. Tetrahedral ClO ₄ ^? anion in I is disordered. In I, the H atom of the NO ₃ ^? ·HNO₃ dimer is split over two close positions with occupation factors of 0.33 and 0.67; this dimer is joined by a very strong single disordered hydrogen bond N-O-H?O = N between the molecule of nitric acid and its anion.     

4,7,13,16,21,24-Hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane Penta(nitrato)lanthanate(III): Synthesis and Crystal Structure

A new complex salt, 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane penta(nitrato)lanthanate(III) (H₂(Crypt-222)]²⁺ · [La(NO₃)₅]^2?), is synthesized. Its crystal structure is studied using X-ray diffraction analysis (space group Pbcm, a = 9.517 Å, b = 13.358 Å, c = 24.585 Å, Z = 4; direct method, full-matrix least-squares in the anisotropic approximation, R = 0.039 for 4650 measured independent reflections). The [La(NO₃)₅]^2? complex anion lies on the m plane, and the 2 axis passes through the 2.2.2-cryptand dication with two protonated nitrogen atoms. The coordination polyhedron of the La³⁺ cation (coordination number 11) is a distorted octahedron with five bifurcated vertices, each containing two O atoms from the same NO ₃ ^? . ligand. The [La(NO₃)₅]^2? anions are joined into infinite polymer chains along the y axis through the NO ₃ ^? bridging ligand.     

Degradation of trichloroethylene in aqueous solution by persulfate activated with Fe(III)–EDDS complex

In this study, an environmentally friendly complexing agent, S,S′-ethylenediamine-N,N′-disuccinic acid (EDDS), was applied in Fe(III)-mediated activation of persulfate (PS), and the degradation performance of trichloroethylene (TCE) was investigated. The effects of PS concentration, Fe(III)/EDDS molar ratio, and inorganic anions on TCE degradation were evaluated, and the generated reactive oxygen species responsible for TCE removal were identified. The results showed that nearly complete TCE degradation was achieved with PS of 15.0 mM and a molar ratio of Fe(III)/EDDS of 4:1. An increase in PS concentration or Fe(III)/EDDS molar ratio to a certain value resulted in enhanced TCE degradation. All of the anions (Cl^?, HCO₃ ^?, SO₄ ^2?, and NO ₃ ^? ) at tested concentrations had negative effects on TCE removal. In addition, investigations using radical probe compounds and radical scavengers revealed that sulfate radicals (SO ₄ ^·? ), hydroxyl radicals (^·OH), and superoxide radical anions (O ₂ ^·? ) were all generated in the Fe(III)–EDDS/PS system, and ^·OH was the primary radical responsible for TCE degradation. In conclusion, the Fe(III)–EDDS-activated PS process is a promising technique for TCE-contaminated groundwater remediation.     

Crystal and molecular structures and luminescence properties of [Eu(Cin)<Subscript>3</Subscript>]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> complex

The crystal structure of europium cinnamate of the composition [Eu(Cin)₃] _n (Cin is cinnamic acid anion C₉H₇O ₂ ^? ) was determined by X-ray crystallography (a = 22.626(1) Å, c = 7.7330(7) Å, space group R3/c, Z = 3, ρ_calc = 1.448 g/cm³). The coordination polyhedron of Eu atoms is a distorted trigonal prism with three centered square faces. The structure is built of infinite polymeric chains [Eu(Cin)₃] _n running along the c axis and linked by van der Waals and π stacking interactions. Luminescent characteristics of the compound were determined.     

Crystal structure of Cs[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)] · H<Subscript>2</Subscript>O

Single crystals of Cs[(UO₂)₂(C₂O₄)₂(OH)] · H₂O were synthesized and structurally studied using X-ray diffraction. The compound crystallizes in monoclinic space group P2₁/m, Z = 2, with the unit cell parameters a = 5.5032(4) Å, b = 13.5577(8) Å, c = 9.5859(8) Å, β = 97.012(3)°, V = 709.86(9) ų, R = 0.0444. The main building units of crystals are [(UO₂)₂(C₂O₄)₂(OH)]^? layers of the A₂K ₂ ⁰² M² (A = UO ₂ ²⁺ , K⁰² = C₂O ₄ ^2? , and M² = OH^?) crystal-chemical family. Uranium-containing layers are linked into a three-dimensional framework via electrostatic interactions with outer-sphere cations and hydrogen bonds with water molecules.     

Copper(II) trinuclear complex with trimesic acid salicylidene hydrazone: Synthesis,structure, and magnetic properties

A trinuclear copper(II) complex of trimesic acid salicylidene hydrazone (H₆L) having the composition [Cu₃L · 4Py] · CH₃OH was synthesized and characterized. By X-ray crystallography, the crystals are triclinic: a = 11.7940(4) Å, b = 13.7241(5) Å, c = 15.8993(6) Å, α = 107.4120(10)°, β = 94.2900(10)°, γ = 105.5650(10)°, space group \(P\bar 1\), Z = 2. The number of symmetrically unique reflections having I > 2σ(I) is 7636, R = 0.0465, and R _w = 0.1198. The newly prepared complex contains, in its unit cell, two [Cu₃L · 4Py] molecules which are linked to form a dimer on account of phenoxo bridges (the Cu-O bond length is 2.555 the Cu…Cu distance is 3.348 Separations between them are 9.414, 9.371, and 9.667 of temperature is satisfactorily fitted in terms of a triangular cluster model (?2J = 2.2 cm^?1) with extra intermolecular interactions (zJ′ = 0.4 cm^?1). EPR spectra of solutions at 360–380 K feature a poorly resolved HFS, whose modeling gives a satisfactory result with allowance for the interaction of unpaired electrons with three equivalent copper nuclei (g = 2.098; a _Cu = 25.8 × 10^?4 cm^?1).     

Solution Thermodynamics of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis><Superscript>/</Superscript>-Ethylenebis-(salicylideneiminato)-diaquochromium(III) Chloride in Aqueous Dimethylsulphoxide

The densities, viscosities and refractive indices of N,N ^/-ethylene-bis(salicylideneiminato)-diaquochromium(III) chloride, [Cr(salen)(H₂O)₂]Cl, in aqueous dimethylsulfoxide (DMSO) with different mass fractions (w ₂ = 0.20, 0.40, 0.60, 0.80 and 1.00) of DMSO were determined at 298.15, 308.15 and 318.15 K under atmospheric pressure. From measured densities, viscosities and refractive indices the apparent molar volumes (V _φ ), standard partial molar volume (V _φ ⁰ ), the slope (S _V ^* ), standard isobaric partial molar expansibility (φ _E ⁰ ) and its temperature dependence (?φ _E ⁰ /?T) _p , the viscosity B-coefficient, its temperature dependence (?B/?T), solvation number (S _n ) and apparent molar refractivity (R _D ^φ ), etc., were calculated and discussed on the basis of ion–ion and ion–solvent interactions. These results revealed that the solutions are characterized by ion–solvent interactions rather than by ion–ion interactions and the complex behaves as a long range structure maker. Thermodynamics of viscous flow was discussed in terms of transition state theory.     

Copper(II) coordination compounds with 8-quinolinaldehyde semicarbazone: Synthesis and structure

A series of compounds of the general formula Cu(HL)X₂ · nH₂O (compound I, X = ClO₄, n = 3; compound II, X = NO₃, n = 2; compound III, X = Cl, n = 0.5; compound IV, X = 1/2SO₄, n = 0) is isolated by the reactions of the copper(II) salts with quinolinaldehyde semicarbazone (HL). Regardless of the reactant ratio, only the compounds with a metal to ligand mole ratio of 1: 1 are formed, where the organic reactant is coordinated in the molecular form. The X-ray diffraction analyses of the [Cu(HL)(NO₃)(H₂O)](NO₃) · H₂O (II) and [Cu(HL)Cl₂] · 0.5H₂O(III) compounds show their substantially different organizations of the molecular structures depending on the specifics of the acido ligand. An ionic structure with one NO ₃ ^? anion incorporated into the inner coordination sphere of the metal as a bidentate chelate ligand is observed in compound II. Molecular tetragonal pyramidal complexes associated into a dimer due to the bridging function of one coordinated Cl^? anion are formed in structure III. The coordination polyhedron of the copper atom in structures II and III is an asymmetrically extended tetragonal bipyramid. The CuClCu angle equal to 90° and the distance between two planes in compound III equal to 2.978 Å determine the insignificant antiferromagnetic interaction in this compound (g = 2.1, J = ?2.5 cm^?1).