Volume 44, Nº 12 (2018)

The reaction of (p-cymene)Ru(Me₂Im)Cl₂ with excess Me₂ImCO₂ in acetonitrile in the presence of NH₄PF₆ afforded the amino complex [(p-cymene)Ru(Me₂Im)(NH₃)Cl]PF₆. The reaction of (p‑cymene)Ru(Me₂Im)Cl₂ with excess anhydrous SnCl₂ gave the complex (p-cy-mene)-Ru(Me₂Im)Cl(SnCl₃), whereas treatment of dimeric iodide complex [(p-cymene)RuI₂]₂ with Me₂ImCO₂ in acetonitrile gave the ionic compound [Me₂ImH][(p-cymene)RuI₃]. CIF files: CCDC nos. 1841649 (I), 1841650 (II), 1841648 (III).

Prismatic crystals of Ag₃(4-Amba)₂(NO₃)₂ (I) and Ag(4-AmbaH)NO₃ (II) are isolated from the reaction mixture of aqueous solutions of 4-aminomethylbenzoic acid (4-AmbaH) and AgNO₃ at Т ≈ 70°C. The crystal structure of compound I (СIF file CCDC no. 1851513) and the luminescence properties of compounds I and II are studied. The structure of compound I contains two crystallographically nonequivalent silver atoms Ag(1) and Ag(2) with the octahedral coordination mode (with allowance for Ag···Ag contacts) with different compositions of the internal spheres of the central atoms. Owing to the contacts, the silver atoms are joined into infinite cluster ribbons (Ag···Ag 3.06−3.27 Å). The carboxylate group of the 4-Amba anion exhibits the bridging properties and binds the silver atoms of both types. The Ag(2) atoms also contact with the oxygen atom of the \({\text{NO}}_{{\text{3}}}^{-}\) ion and coordinate the NH₂ group of 4-Amba. The photoluminescence spectra of compounds I and II are of the same type and show the presence of two groups of emission bands with centers at 484 and 543 nm shifted to the red range of the spectrum relative to the band of 4-AmbaH.

The distribution of the electron density function in crystals of {[ZnBpe(Me₂Mal)] · H₂O}_n (I) and [Zn(H₂O)₄Bpe₂](HEt₂Mal)₂ (II) is obtained by the periodic DFT calculations. Under UV irradiation, compounds I and II transform into [Zn(Bpe)(Me₂Mal)]₂[Zn₂(Тpcb)(Me₂Mal)₂] · H₂O and {[Zn(H₂O)₄(Bpe)₂]_0.15[Zn(H₂O)₄(Tpcb)]_0.85(HEt₂mMal)₄} (Bpe is 1,2-bis(4-pyridine)ethylene, Тpcb is 1,2,3,4-tetrakis(4-pyridine)cyclobutane, H₂Me₂Mal is dimethylmalonic acid, and H₂Et₂Mal is diethylmalonic acid), respectively. An analysis of intermolecular contacts using Bader’s “Atoms-in-Molecules” theory shows the bonding route and bond critical point between the carbon atoms of the adjacent 1,2-bis(4-pyridine)ethylene molecules. It is established that the common surface of the Voronoi–Dirichlet molecular polyhedra between the photosensitive fragments can serve as a criterion for the possible participation of the molecules in solid-phase photoinduced reactions.

The reactions of thiocyanates Ln(NCS)₃ ⋅ 6H₂O (Ln = Y, Eu, and Tb) with 2,4,6-tris(2-pyridyl)-s-triazine (Tptz) in МеОН, MeCN, and H₂O afford neutral or ionic thiocyanate complexes with one coordinated Tptz molecule. The uniqueness of the complexes is the presence of the second Tptz molecule in the exo coordination. The transformation of Tptz into the endo coordination occurs upon recrystallization from an aprotic solvent. The structural peculiarities of the synthesized compounds are determined by powder X-ray diffraction, IR spectroscopy, and single-crystal X-ray diffraction (CIF files CCDC nos. 1827916–1827921).

Complexes Ph₃(C₂H₄O₂)Sb⋅⋅⋅DMSO (I), (3-FC₆H₄)₃(C₂H₄O₂)Sb⋅⋅⋅DMSO (II), and (4‑MeC₆H₄)₃-(C₆H₄O₂)Sb⋅⋅⋅DMSO (III) are synthesized by the reactions of triarylantimony with ethylene glycol or pyrocatechol in the presence of an oxidant and dimethyl sulfoxide (DMSO). According to the X-ray diffraction analysis data, the Sb atoms in the complexes have the coordination of a distorted octahedron with the chelate cycle (C₂H₄O₂ or C₆H₄O₂) and two aryl groups in the equatorial plane, and the third aryl group and DMSO molecule occupy the axial positions. The СSbO axial angles are 173.59(5)° (I); 175.96(8)°, 175.93(8)° (II); and 174.07(8)° (III). The Sb⋅⋅⋅О=SMe₂ distances (2.346(2)−2.407(2) Å) considerably exceed the sum of covalent radii of the atoms.

Two structurally similar new oxovanadium complexes, [VO(L)(L¹)] (I) and [VO(L)(L²)] (II), where L is the dianionic form of 3-((3-bromo-2-hydroxyphenyl)-{[1-(3-bromo-2-hydroxyphenyl)methylidene]amino}methyl)pentane-2,4-dione (H₂L), L¹ is the deprotonated form of 8-hydroxyquinoline, L² is 2,2'-bipyridine, were prepared and characterized by spectroscopic and single crystal X-ray diffraction (СIF files CCDC nos. 1566824 (I), 1566825 (II)). Complex I crystallizes as the monoclinic space group P2₁/c with unit cell dimensions a = 11.265(1), b = 18.179(2), c = 13.461(2) Å, β = 103.376(3)°, V = 2681.8(5) Å³, Z = 4, R₁ = 0.0659, wR₂ = 0.1318, GOOF = 1.003. Complex II crystallizes as the orthorhombic space group Pbca with unit cell dimensions a = 19.958(1), b = 13.600(1), c = 22.8713(2) Å, V = 6192.3(8) ų, Z = 8, R₁ = 0.0550, wR₂ = 0.1008, GOOF = 1.074. X-ray analysis indicates that the complexes are mononuclear oxovanadium(V) species with the V atoms in octahedral coordination. The complexes were evaluated for their antibacterial (Bacillus subtilis, Staphylococcus aureus, Escherichia coli, and Pseudomonas fluorescence) and antifungal (Candida albicans and Aspergillus niger) activities by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide) method. Interestingly, complex II has strong activity against S. aureus.

Two new alkaline earth metal coordination polymers, which are [Ba(H₂IDC)-(H₃HmIDC)(H₂O)₂]_n (I) and [Sr(H₂HmIDC)]_n (II) [H₃IDC = 1H-imidazole-4,5-dicarboxylic acid, H₄HmIDC = 2-(hydroxymethyl)-1H-imidazole-4,5-dicarboxylic acid), respectively, have been successfully synthesized under solvothermal conditions by employing H₄HmIDC as the starting material. Both compounds I and II were structurally characterized by diverse techniques, such as single crystal X-ray diffraction (CIF files CCDC nos. 1839705 (I) and 1839706 (II)), FT-IR spectra, powder X-ray diffraction, and thermogravimetric analyses. Compound I exhibits a two-dimentional (2D) coordination network with a (4, 4) topology based on dinuclear [Ba₂O₄] as second building units (SBUs). Whereas compound II features a 3D coordination framework based on infinite 1D inorganic chains as SBUs, which can be further simplified as a 5‑connected noy topology. In addition, the photoluminescent properties of both compounds I and II were also investigated.

A series of silver alkynyl cages were synthesized using ligand 3,5-di-tert-butyl-phenylethynide and were structurally characterized. Reaction with [Ag(ArC≡C)]_n polymer and (ⁿBu₄N)X (X = F, Cl, Br) gave compounds incorporating different halogen anions (F⁻, Cl⁻, Br⁻) and a hollow compound, namely [Ag₁₄(ArC≡C)₁₂(MeCN)₆](OTf)₂ · 4MeCN (I), [Ag₁₄(ArC≡C)₁₂(EtOH)₂F]F · EtOH (II), [Ag₁₄(ArC≡C)₁₂(THF)₂Cl]OH · THF (III) and [Ag₁₄(ArC≡C)₁₂(MeCN)₄Br]OH (IV) (ArC≡C = 3,5-di-tert-butyl-phenylethynide). Direct synthesis of anion containing cages and indirect synthesis from the hollow cage were achieved. Structural studies (CCDC nos. 1831128 (I), 1831129 (II), 1831130 (III), and 1831131 (IV)) revealed that the incorporation of anions reduced the mean Ag−Ag bond length and therefore the cage size, giving the order of F@Ag₁₄ ≈ Cl@Ag₁₄ < Br@Ag₁₄ < halogen-free. The cage size was larger than those of similar Ag₁₄ clusters reported previously, which is likely due to the use of bulky alkynyl ligands.

A new heterometallic-organic framework, namely [PbCa(Mbdc)₂(DMF)]_n (I) (H₂Mbdc = isophthalic acid, DMF = N,N'-dimethylformamide), was synthesized by the solvothermal reactions of Pb(NO₃)₂, Ca(NO₃)₂ · 4H₂O and H₂Mbdc. Single crystal X-ray diffraction analysis (CIF file CCDC no. 1567197) revealed that compound I features a 3D pillar-layered framework with 2D inorganic Pb–O–Ca connectivity. Thermal analysis indicated that the framework of compound I can be stable up to 320°C, and luminescent property investigation indicated that compound I exhibits intense luminescence at room temperature.