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Vol 45, No 2 (2019)
- Year: 2019
- Articles: 11
- URL: https://journals.rcsi.science/1070-3284/issue/view/13358
Article
New Zn(II) and Cd(II) Coordination Polymers with 1,2-Benzenedicarboxylic Acid: Synthesis and Structures
Abstract
1,2-Benzenedicarboxylic (phthalic) acid (1,2-BdcН2) and bipyridine ligands are used for the synthesis of the Zn(II) and Cd(II) coordination polymers. As a result, the target assembling of four complexes is carried out. The structures of the synthesized complexes are studied by X-ray diffraction analysis. Three of the obtained compounds are new coordination polymers [Zn2(1,2-Bdc)2(Bpe)2]n · 0.25n(Dmf) · 0.25nH2O (I), [Zn2(1,2-Bdc)2(Bpp)2]n (II), and [Cd(1,2-Bdc)(Bpp)(H2O)]n (III) (Bpe is bis(4-pyridyl)ethane, Bpp is 1,2-bis(4-pyridyl)propane, and Dmf is dimethylformamide) (CIF files CCDC nos. 1824264 (I), 1824265 (II), and 1824266 (III)), and the fourth one is the known Cd(II) compound [Cd(1,2-Bdc)(H2O)]n. The study of the structures of compounds I–III reveals the dimensionalities of the polymers: 3D for the Zn(II) polymer and 2D for the Cd(II) polymer. Different shapes of the coordination polyhedra of Zn(II) are found in compounds I and II, and different coordination modes of the doubly deprotonated ligand (1,2-Bdc)2– to the metals are observed in compounds I–III.
81-91
Complex of Cadmium(II) Iodide with 3,4-Diphenyl-1-(Pyridin-2-yl)-6,7-Dihydro-5H-Cyclopenta[c]pyridine: Synthesis and X-ray Diffraction Study
Abstract
The structure of the cadmium(II) iodide complex with 3,4-diphenyl-1-(pyridin-2-yl)-6,7-dihydro-5H-cyclopenta[c]pyridine is studied and determined by X-ray diffraction analysis (СIF file CCDC no. 1833097). The problem about the possibility of coordination of the phenyl substituents of the ligands to the central cadmium atom is examined. The degree of participation of the π system of the phenyl substituent of the ligand in the coordination to the central ion is analyzed using quantum chemical calculations.
92-96
Synthesis and Characterization of Coordination Compounds of 3d-Metal Malonates with Phenylacetyl Hydrazide. Crystal Structure of [Cu(L)2][Cu(Mal)2] · 4.5H2O (L Is Phenylacetyl Hydrazide, Mal2– Is Malonic Acid Anion)
Abstract
Three phenylacetyl hydrazide malonate complexes [M(L3)](Mal) of cobalt(II) (I), nickel(II) (II), and zinc(II) (III), as well as complex [Cu(L)2][Cu(Mal)2] ⋅ 4.5H2O (IV) are synthesized. The obtained compounds are characterized by chemical analysis, IR spectroscopy, diffuse reflectance spectroscopy, and thermogravimetry. Compound IV (where L is phenylacetyl hydrazide, and Mal2– is malonic acid anion) is studied by X-ray diffraction analysis (CIF file CCDC no. 1844502).
97-104
Computational Modeling of Spin-Crossover in Mixed-Ligand Binuclear Iron and Cobalt Complexes with 5,6-Bis(salicylideneimino)-1,10-Phenanthroline
Abstract
The quantum chemical modeling (DFT UTPSSh/6-311++G(d,p)) of the binuclear homo- and heterometallic Fe and Co complexes based on the 5,6-bis(salicylideneimino)-1,10-phenanthroline ligand and two bipyridyl molecules is performed. The magnetic properties of these compounds can be switched due to the thermally induced spin-crossover occurring at the cobalt ions. The predicted energetic and magnetic characteristics of isomers of the studied systems allow one to consider them as promising molecular switches.
105-111
1-(2-Methoxyphenyl)-1,4-Dihydro-5H-Tetrazole-5-Thione and Its Complex with Cd(II): Molecular and Crystal Structures
Abstract
The molecular and crystal structures of 1-(2-methoxyphenyl)-1,4-dihydro-5H-tetrazole-5-thione (L) and its complex with cadmium(II) (II) are studied by X-ray diffraction analysis (CIF files CCDC nos. 1567109 (L) and 1547252 (II)). Free ligand L is nonplanar thione. The dihedral angle between the tetrazole and benzene cycles is 85.21(7)°. These cycles form centrosymmetric dimers in the crystal by two hydrogen bonds N–H···S. The dimers contain the central planar eight-membered ring {S=C–N–H···S=C–N–H···}. Complex II has a chain structure of the composition [(C8H7N4OS)2Cd]n. The coordination mode of the Сd(II) atom is a distorted tetrahedron consisting of two nitrogen atoms and two sulfur atoms of four ligands L. The 1D chains contain the eight-membered rings {←S=C–N–Cd ← S=C–N–Cd} in the boat conformation. Weak intermolecular hydrogen bonds C–H···N are observed between the adjacent 1D chains along the c axis in the crystal.
112-118
New Method for the Synthesis of Octahedral Rhenium Chalcocyanide Cluster Complexes [{Re6(μ3-Q)8}(CN)6]4– (Q = S, Se, Te)
Abstract
A new method is proposed for the synthesis of the octahedral rhenium chalcocyanide cluster complexes [{Re6(μ3-Q)8}(CN)6]4– (Q = S, Se, Te) using rhenium(IV) oxide as the starting compound. Among the synthesized compounds, the anhydrous cluster salt K4[{Re6Se8}(CN)6] is characterized by X-ray diffraction analysis for the first time. The crystals are orthorhombic, space group Pbcn; a = 13.1386(13), b = 11.4941(8), c = 17.2990(16) Å, Z = 4, V = 2612.4(4) Å3 (CIF file IСSD no. 434320). The crystal structure of K4[{Re6Se8}(CN)6] represents a framework type packing based on the K+ cations coordinated by the cyanide groups of the cluster anions [{Re6Se8}(CN)6]4–.
119-123
Metallocenyl-containing and Unsaturated Fulleropyrrolidine Derivatives: Synthesis and Hydrogenation
Abstract
The possibility of Pd/C-catalyzed hydrogenation of ferrocenyl, cymantrenyl, and ruthenocenyl derivatives of N-methyl-2-(3-chlorovinyl)fulleropyrrolidine and N-methyl-2-(2-styryl)fulleropyrrolidine with hydrogen was elucidated. A new compound, N-methyl-2-(3-chlorovinyl-3-ruthenocenyl)fulleropyrrolidine, was synthesized.
124-127
Mononuclear Sb(V) Bromide Complexes with 3-Halopyridinium Cations: Synthesis, Structures, and Thermal Stability
Abstract
Mononuclear complexes (3-XPyH)[SbBr6] (X = Cl (I), Br (II)) are synthesized by the reactions of Sb2O3, Br2, and 3-XPy in HBr. Compound I is characterized by X-ray structure analysis (СIF file CCDC no. 1818602). The crystals of compounds I and II are isostructural. The thermal stability of the synthesized complexes is studied by thermogravimetry.
128-132
Triphenylantimony(V) Catecholates Based on o-Quinones, Derivatives of Benzo[b][1,4]-Dioxines and Benzo[b][1,4]-Dioxepines
Abstract
New catecholate complexes of triphenylantimony(V), (Etgly-3,6-DBCat)SbPh3 (I), (Propgly-3,6-DBCat)SbPh3 (II), and (Cat-3,6-DBCat)SbPh3 (III), based on analogs of sterically hindered 3,6-di-tert-butyl-o-benzoquinone, 5,8-di-tert-butyl-2,3-dihydrobenzo[b][1,4]dioxine-6,7-dione (L1), 6,9-di-tert-butyl-2,3-dihydrobenzo[b][1,4]dioxepine-7,8-dione (L2), and 1,4-di-tert-butyl-dibenzo[b,e][1,4]dioxine-2,3-dione (L3), which are the 2,3-dihydrobenzo[b][1,4]dioxine, 2,3-dihydrobenzo[b][1,4]dioxepine, and dibenzo[1,4]dioxine derivatives, respectively, have been synthesized. At room temperature catecholates I and II react with molecular oxygen adding an O2 molecule to form the corresponding spiroendoperoxides IV and V. Catecholate III reacts with oxygen with the deep oxidation of the complex and formation of neutral o-benzoquinone. The molecular structures of complexes I and III are determined by X-ray diffraction analysis (CIF files CCDC nos. 1840299 (I · toluene) and 1840300 (III)).
133-141
The Different Effects of Metal Ions on the Synthesis of Macroacyclic Compounds: X-ray Crystal Structure, Theoretical Studies, Antibacterial and Antifungal Activities
Abstract
In this work, we have been involved studying the synthesis of some new macroacyclic complexes I–VIII, so we tried to get propoesed results in all cases but in the case of compound I, according to X-ray crystal structure, the product is a protonated Schiff base. By the reaction of a 1 : 1 (metal : ligand) stoichiometry of two known Schiff base ligands, 1,2-bis(2-((2-hydroxy ethylimino)methyl)phenoxy)ethane (H2L1) or 1,3-bis(2-((2-hydroxyethylimino)methyl) phenoxy)propane (H2L2) and appropriate metal salts in methanol in the case of Ni2+, Cu2+ and Co2+, macroacyclic complexes were prepared. When using Mn2+ only protonated Schiff base ligands is the final product. All compounds were characterized by microanalysis and IR spectroscopy, whereas compound I was also characterized by single crystal X-ray. The X-ray structure of compound I showed that both protonated imines are neutralized by two perchlorate ions. Computational calculations of relevant complexes are done by using one of the hybrid density functional theories which are a B3LYP method with 6-31G(d) basis set in a vacuum. Also, the synthesized compounds were screened for their antibacterial activities against nine bacterial strains and showed antibacterial effects. These complexes also showed antifungal effects on two species of Candida.
142-153
Syntheses, Crystal Structures, and Antibacterial Activity of Mononuclear Vanadium(V) Complexes with Aroylhydrazone and Pyrone as Mixed Ligands
Abstract
Two mononuclear vanadium(V) complexes, [VOL1(KA)] (I) and [VOL2(EM)] (II), where L1 and L2 are the dianionic form of N'-(3-ethoxy-2-hydroxybenzylidene)-4-methoxybenzohydrazide (H2L1) and 4-bromo-N'-(3-ethoxy-2-hydroxybenzylidene)benzohydrazide (H2L2), respectively; KA and EM are the monoanionic form of kojic acid and ethyl maltol, respectively, were prepared. The complexes were characterized by elemental analysis, IR and UV-Vis spectra, and single crystal X-ray determination (CIF files CCDC nos. 1823339 (I) and 1823341 (II)). The crystal of complex I crystallizes in the triclinic space group P–1 with unit cell a = 7.7813(16), b = 11.297(2), c = 14.3390(18) Å, α = 90.449(2)°, β = 100.402(2)°, γ = 108.366(2)°, V = 1173.8(4) Å3, Z = 2. The crystal of complex II crystallizes in the monoclinic space group P21/n with unit cell a = 8.6935(5), b = 30.9695(18), c = 18.4469(11) Å, β = 99.366(2)°, V = 4900.3(5) Å3, Z = 8. The V atoms in the complexes are in octahedral geometry. The antimicrobial activities of the compounds against K. pneumoniae, S. aureus, P. aeroginosa, E. coli, and B. subtilis were investigated.
154-162