Russian Journal of Coordination Chemistry最新文献

N-Benzyloxycarboxamides (HL) and corresponding zirconium(IV) complexes [Zr(L)₄] (L = R'C(O)NOR, R = CH₂–C₆H₅; R' = CH₃ for L = baa or R' = C₆H₅ for L = bba) are synthesized and characterized to reveal the influence of the aromatic substituent on the structures and thermal properties. The structures of Hbba, [Zr(baa)₄], and [Zr(bba)₄] (CIF files CCDC nos. 2 474 365, 2 474 366, and 2 474 367, respectively) are determined by single-crystal X-ray diffraction (SC-XRD) and compared with those of N‑methoxybenzamide analogues Hmba and [Zr(mba)₄] (R = CH₃, R' = C₆H₅). The compounds are also studied by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The thermodynamic parameters for melting of Hbba and [Zr(baa)₄] have been determined for the first time. In the [Zr(L)₄] complexes, the introduction of the benzyl group into L results in the disappearance of the low-temperature structural transitions (L = mba) and a decrease in the melting points (L = baa, bba). The melting points of N‑alkoxybenzamides increase in the order L = mba < bba. Under the TGA conditions at comparable molecular weights, the [Zr(mba)₄] complex partially evaporates, whereas [Zr(baa)₄] decomposes.

The reaction of zinc(II) nitrate with 2-ferrocenyl-1,10-phenanthroline (L) produced the complex [ZnL(NO₃)₂] (I), which was analyzed by elemental analysis, powder X-ray diffraction, thermogravimetric analysis, cyclic voltammetry, and IR spectroscopy. According to the single-crystal X-ray diffraction analysis, the coordination environment of zinc(II) can be described as 5 + 1, and L acts as a chelating ligand that binds to the zinc(II) atom through the nitrogen atoms of the phenanthroline moiety. The cytotoxic properties of complex I were evaluated using the human two-dimensional cell lines Hep2 (laryngeal carcinoma cells), A549 (lung adenocarcinoma cells), and MRC5 (nontumor lung fibroblasts). Complex I exhibited cytotoxicity at concentrations between 50 and 100 μM. The activity of complex I in Hep2 spheroids (3D model) was found to be comparable to that in the two-dimensional model. The behavior of the complex in solution was studied using optical spectroscopy, conductometry, and cyclic voltammetry.

The crystals of R[UO₂(mac)₃]₂ (where R is (CH₃)₂({text{NH}}_{2}^{ + }) (I) or (C₂H₅)₂({text{NH}}_{2}^{ + }) (II), and mac is methacrylate ion ({{{text{C}}}_{{text{4}}}}{{{text{H}}}_{{text{5}}}}{text{O}}_{{text{2}}}^{ - })) are synthesized and studied by IR spectroscopy and X-ray diffraction (XRD) (CIF files CCDC nos. 2476810 (I) and 2476811 (II)). The [UO₂(mac)₃]^– complexes have the crystallochemical formula А(B⁰¹)₃, where A is ({text{UO}}_{2}^{{2 + }}), and B⁰¹ is mac. A comparative analysis of noncovalent interactions in the crystal structures of compounds I and II is carried out using the Voronoi–Dirichlet molecular polyhedra (VDMP) and Hirshfeld surface methods. The results of these independent methods are well consistent for both qualitative and quantitative estimations of intermolecular contacts. Only the VDMP method allows one to characterize in detail any interatomic contacts that contribute to the real range of intermolecular interactions.

The study addresses mixed-anion Eu(III) complexes with benzoic (Bz) and pentafluorobenzoic (Pfb) acid anions and 2,2'-bipyridine(Bpy), 4,4'-dimethyl-2,2'-bipyridine (Me₂Bpy), 4,4'-di-tert-butyl-2,2'-bipyridine (t-Bu₂Bpy), 4,4'-dinonyl-2,2'-bipyridine(Nn₂Bpy), and 3,4,7,8-tetramethyl-1,10-phenanthroline: [Eu₂(Bpy)₂(Pfb)_2.4(Bz)_3.6] (I), [Eu₂(Me₂Bpy)₂(Pfb)_2.5(Bz)_3.5] (II), [Eu₂(Nn₂Bpy)₂-(Pfb)_3.5(Bz)_2.5]·2MeCN (III), [Eu₂(t-Bu₂Bpy)₂(Pfb)_5.5(Bz)_0.5]_n·2nMeCN (IV), and [Eu₂(Me₄Phen)₂-(Pfb)_4.8(Bz)_1.2]_n (V). According to X-ray diffraction data, in the structures of all compounds, Bz^– and Pfb^– anions are refined simultaneously in various ratios in some anion sites. It was shown that varying the substituents in the N-donor ligands affects the composition and geometry of the formed complexes. The complexes were characterized by X-ray diffraction, IR spectroscopy, and CHN analysis. The structures and crystal packing of the obtained complexes were analyzed in detail. The major contribution to stabilization of the crystal packing is made by π···π, C–H···F, and C–F···π interactions.

Specific features of the structures of five various complexes [Y(Me₃tach)Cl₃(THF)₂] (I), [Y(Me₃tach)₂Cl₃] (II), [Y(Me₃tach)Cl₂(μ-Cl)₂YCl₂(THF)₃] (III), [Y(Me₃tach)Cl₃(THF)]₂ (IV), and [Y(Me₃tach)₂Cl₂]⁺[Y(Me₃tach)Cl₄]^– (V) formed via the reaction of yttrium chloride tetrahydrofuranate with 1,3,5-trimethyl-1,3,5-triazacyclohexane (Me₃tach) are compared. The molecular structures of newly synthesized complexes IV and V are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 2484944 and 2484945, respectively). All complexes, except for complex V, demonstrate similar metal–ligand distances with a correction to the difference in coordination numbers regardless of the structure of the complex and metal to ligand ratio for both mono- and binuclear complexes.

The reaction of 3,3-bis(3,5-dimethylpyrazol-1-yl)-1-phenylpropan-1-one (L) with cobalt(II) chloride and copper(II) chloride yielded neutral, isostructural heteroligand complexes [LMCl₂] with M = Co for I and M = Cu for II. Their structures were determined by direct X-ray diffraction methods (CCDC nos. 2478389 for I, 2478390 for II). In both complexes, the metal center has a tetrahedral coordination environment, and L coordinates to the metal ion in a bidentate manner.

The reaction of 3,5-disubstituted pyrazoles with ferrocenylvinyl ketone 1 produced new ferrocenoylpyrazoles 3a–3e. The reaction of 1 with unsymmetrical 3(5)-methyl-5(3)-trifluoromethylpyrazole gave both isomers, with their ratio depending on the reaction conditions. Both isomers 3d and 3e were isolated in pure form and characterized by mass spectrometry, NMR spectroscopy, and cyclic voltammetry. The structure of isomer 3e, which is the product of thermodynamic control, was confirmed by X-ray diffraction analysis (CCDC no. 2450072).

Five new bromide complexes of antimony(III) and bismuth(III) with dicationic species (3‑ClPyC₆)[SbBr₆]₂ (I), (3-ClPyC₆)₂[Sb₄Br₁₆] (II), (3-ClPyC₆)₃[Bi₂Br₉]₂ (III), (3-BrPyC₆)₃[Sb₂Br₉]₂ (IV), and (3-BrPyC₆)₃[Bi₂Br₉]₂ (V) based on substituted 3-halopyridines {(3-XPy)₂(CH₂)₆}²⁺ (X = Cl, Br) were obtained. The structures of the compounds were determined by X-ray diffraction analysis (CCDC nos. 2457726–2457730). The features of halogen···halogen interactions between the cations and anions were analyzed.