Syntheses, structures and properties of five copper coordination polymers constructed by the triazole ligand

Reactions of different metal salts with 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-abpt) gave rise to five new complexes, namely [Cu₄(CN)₄(3-abpt)₂]_n (1), [CuBr(3-abpt)]_n (2), [CuI(3-abpt)]_n (3), [Cu₃I₃(3-abpt)]_n (4) and [Cu(3-abpt)(SO₄)(H₂O)]_n (5). Compounds 1, 3, 4 and 5 are all 2D structures. Compound 1 is a double-layered polymer with an uncommon 3-nodal 3-connected (10³)(10².4)₄ network, 3 shows a 2D square layered structure, 4 is also a double-layered polymer with 2-nodal 4-connected (3.4.5.6².7)₂(3.4².5².7) network and 5 is a 2D structure which is ultimately stacked with an ABAB repeat pattern. Compound 2 is a 1D coordination polymer which exhibits a ladder-like network. The photoluminescence of 1-2 has also been investigated. The long emission lifetimes of 1-2 could be assigned to metal-to-ligand charge transfer triple excited states [MLCT].     

Synthesis and structures of two molybdenum(VI) complexes derived from similar benzohydrazone ligands with catalytic properties

Two new structurally similar molybdenum(VI) complexes, [MoO₂L¹(CH₃OH)] (1) and [MoO₂L²(CH₃OH)] (2), where L¹ is the dianionic form of N′-(2-hydroxy-5-nitrobenzylidene)-2-methylbenzohydrazide and L² is the dianionic form of N′-(2-hydroxy-4-methoxybenzylidene)-2-methylbenzohydrazide, were prepared and structurally characterized by elemental analysis, infrared spectra, and single-crystal X-ray diffraction. 1 crystallizes in the monoclinic space group P2₁/c, with unit cell dimensions a?=?7.941(1), b?=?14.337(2), c?=?15.141(2)?Å, β?=?92.782(2)°, V?=?1721.8(4)?ų, Z?=?4, R₁?=?0.0286, wR₂?=?0.0650, GOOF?=?1.028. 2 crystallizes in the triclinic space group P-1, with unit cell dimensions a?=?8.003(1), b?=?10.608(1), c?=?10.880(1)?Å, α?=?95.745(2)°, β?=?97.627(2)°, γ?=?105.762(2)°, V?=?872.0(2)?ų, Z?=?2, R₁?=?0.0226, wR₂?=?0.0595, GOOF?=?1.116. X-ray analysis indicates that Mo in the complexes are coordinated by the phenolate oxygen, imino nitrogen, and enolate oxygen of the benzohydrazone, methanol, and two oxo groups, generating octahedral coordination. The oxidation of olefins with the complexes as catalysts was evaluated, indicating that the complexes showed excellent catalytic efficiency in oxidation of most aliphatic and aromatic substrates under mild conditions using tert-butyl hydrogen peroxide as oxidant.     

Synthesis,crystal structures and anticancer activities of two decavanadate compounds

Two ammonium decavanadate(V) compounds, (H₂tmen)₃V₁₀O₂₈·6H₂O (1) and (H₂en)₃V₁₀O₂₈·2H₂O (2), where H₂tmen and H₂en represent the doubly protonated N,N,N′,N′-tetramethylethylenediammonium ion and doubly protonated ethylenediammonium ion, respectively, have been synthesized and structurally characterized by elemental analyses, spectroscopic (i.r., e.s.r.) studies, and single-crystal X-ray diffraction. Both crystal structures reveal the presence of the [V₁₀O₂₈]⁶⁻ cluster anions, doubly protonated diammonium cations, and lattice water molecules. Hydrogen bonds assemble these two compounds to form three-dimensional networks. The in vitro anticancer activity against A549 and P388 tumor cells lines has also been determined by the MTT-based assay, and the results suggest that both compounds can inhibit proliferation of these two kinds of tumor cells.     

Hydrothermal syntheses and characterizations of two new hydrogen bond-supported supramolecular compounds based on polyoxometalates

Two new polyoxometalates [HN(C₂H₅)₃]₃[PMo₁₂O₄₀] (1) and [NH₂(C₂H₄NH₃)₂]₂[Mo₅P₂O₂₃] (2) have been hydrothermally synthesized and characterized by IR, UV-Vis, XPS spectra, TG analyses, and single crystal X-ray diffraction. Crystal data for 1: monoclinic, space group C2/c, a = 24.651(5) Å, b = 10.822(2) Å, c = 22.413(5) Å, β = 120.37(3)°, and V = 5158.7(18) ų; for 2: triclinic, space group P-1, a = 9.821(2) Å, b = 9.948(2) Å, c = 14.687(3) Å, α = 95.490(3)°, β = 98.870(3)°, γ = 95.710(3)°, and V = 1401.7(5) ų. The crystal structure analyses reveal complex hydrogen bonds in both 1 and 2 in 3-D supramolecular arrays constructed from different polyoxoanions and organic ligands.     

Synthesis,crystal structures,and catalytic properties of phenoxo-bridged dinuclear manganese(III) complexes with bis-Schiff bases

Two structurally similar centrosymmetric phenoxo-bridged dinuclear manganese(III) complexes, [Mn₂(L¹)₂(N₃)₂] (1) and [Mn₂(L²)₂(NCS)₂] (2), were prepared from the tetradentate bis-Schiff base ligands, N,N’-bis(salicylidene)propane-1,2-diamine (H₂L¹) and N,N’-bis(salicylidene)ethane-1,2-diamine (H₂L²), respectively, in the presence of pseudohalides. The complexes have been characterized by FTIR, elemental analyses, and molar conductivity. Structures of the complexes have been confirmed by single-crystal X-ray determination. The bis-Schiff base ligands coordinate with Mn through their phenolate oxygen and imino nitrogen. Each Mn is an octahedral. The complexes showed that they exhibit high activity in catalytic olefin oxidation.     

Synthesis,crystal structures and in vitro anticancer activities of two copper(II) coordination compounds

Transition Metal Chemistry - Two new Cu(II) coordination compounds, [Cu2(cca)(phen)4](ClO4)2(H2O)5.5, 1, and [Cu2(OH)(oda)(phen)2)](ClO4), 2, where cca?=?4-carboxycinnamate;...     

Synthesis and structures of some di- and triferrocenylmethane derivatives

Some triferrocenylmethane derivatives were prepared by reaction of triferrocenylmethanol (5) with triphenylcarbenium tetrafluoroborate followed by a nucleophile. Crystal structure analyses of triferrocenylmethane (7) and of 1,1,1-triferrocenyl-2,2-dimethylpropane (11) show that the conformation adopted by the triferrocenylmethyl group differs significantly with the steric bulk of the substituent at the central carbon atom. Treatment of 1,1′-bis(tributylstannyl)ferrocene (13) with 1 equiv. of butyllithium followed by chloroethylformiate affords complexes with one (14), two (15) or three ferrocenyl units (16) depending on the amount of chloroethylformiate used. Compound 16 is the first triferrocenylmethane derivative with substituents at the opposite cyclopentadienyl ring. Threefold lithiation of this compound is shown to work using butyllithium followed by dimethylformamide.     

Synthesis and crystal structure of a new zinc diphosphonate

A new zinc diphosphonate [NH₃CH(CH₃)CH₂NH₃]₂Zn₂(edbbp)₂(HNO₃)₂·4H₂O [eddbp?= O₃PCH(Ph)NH(CH₂)₂NHCH(Ph)PO₃] was hydrothermally synthesized with Zn(NO₃)₂·6H₂O, ethane-1,2-diamino-N,N′-bis(benzylphosphonic acid) (H₄edbbp) and 1,2-propyldiamine. It consists of a centro-symmetric dimeric unit [Zn₂(edbbp)₂], in which each zinc ion adopts a distorted square-pyramidal coordination geometry. Hydrogen bonds formed between phosphonate groups and protonated 1,2-propyldiamine molecules link the dimeric units into one-dimensional chains. The doubly protonated 1,2-propyldiamine molecules serve not only as charge compensating counter ions, but also as bridging groups. Hydrogen-bonding interactions among the phosphonate oxygen atoms, water molecules, nitric acid molecules and protonated 1,2-propyldiamine result in the formation of a three-dimensional supramolecular network.     

Synthesis of new tetrazole and triazole substituted pyroglutamic acid and proline derivatives

Racemic 4-(substituted-1H-1,2,3-triazol-1-yl), 4-aryl and 4-(arylmethyl)tetrazolyl-pyroglutamic and proline derivatives were synthesized from dimethyl-2,4-dibromoglutaryle 1 in good yield using mild reaction conditions. The key step for the preparation of the triazole substituted molecule was the 1,3-dipolar cycloaddition of an acetylenic compound with an azido derivative. The tetrazole derivatives were prepared by the selective N2-alkylation of 5-substituted tetrazoles with 1.     

Four anthraquinone-1,5-disulfonate-based metal complexes incorporating N-heterocyclic coligands: synthesis,crystal structures,and fluorescence

Four new anthraquinone-1,5-disulfonate (L)-based metal complexes with N,N-bidentate chelating coligands, {[Pb(phen)₂(L)]?·?4H₂O} _n (1), {[Mn₂(2,2′-bipy)₂(H₂O)₆(L)]?·?L?·?6H₂O} (2), [Co(phen)₂(H₂O)(L)] (3), and [Zn(phen)₂(H₂O)(L)] (4) (phen = 1,10-phenanthroline and 2,2′-bipy?=?2,2′-bipyridine), have been hydrothermally synthesized and were structurally characterized by single-crystal X-ray diffraction, elemental analyses, FT-IR spectra, thermogravimetric curves, and solid luminescence spectra. Structural analysis suggests that 1 is a polymeric 1D zigzag chain bridged by dianionic L. In contrast, the other three complexes have discrete centrosymmetric binuclear structure for 2 and isolated isomorphic mononuclear entities for 3 and 4, which are further assembled into 3D supramolecular networks by abundant hydrogen-bonding and/or π–π stacking interactions. Additionally, 2 and 4 exhibit favorable luminescent emissions, suggesting they are potential candidates for light emission materials.     

Fluorine containing coordination compounds of Cr(III)

Trans-[Cr(NH₃)₄F₂]I·H₂O (A) has monoclinic P2_l/m (No. 11) space group witha=5.033 (3),b=16.333 (10),c=5.539 (3) Å and =98.47 (3)°,Z=2.Cis-[Cr(NH₃)₄F₂]ClO₄ (B) has tetragonal space group I4_lmd (No. 109) witha=7.417 (1),c=16.610 (2) Å,Z=4. Cr–F and Cr–N bonding distances are 1.894 (3); 2.087 and 2.083 (5) Å for A and 1.887 (6); 2.062 (5) and 2.051 (7) Å for B. Octahedral angles within the cations are close to 90° for both compounds. Cr–N bondtrans to Cr–F bond in thecis compound is shorter. Structures were refined toR ₂ values of 0.072 (A) and 0.058 (B).Trans-[Cr(NH₃)₄F₂]I·H₂O has weak N–H–F hydrogen bonds between the cations. None such interactions were found incis-[Cr(NH₃)₄F₂]ClO₄.

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Fluorhältige Komplexe des Cr(III), 2. Mitt.: Kristall- und Molekülstruktur von trans-[Cr(NH₃)₄F₂]I·H₂O und cis-[Cr(NH₃)₄F₂]ClO₄

Zusammenfassung Trans-[Cr(NH₃)₄F₂]I·H₂O (A) kristallisiert in der Raumgruppe P2_l/m (No. 11) mitZ=2 unda=5,033 (3),b=16,333 (10),c=5,539 (3) Å und =98,47 (3)°.Cis-[Cr(NH₃)₄F₂]ClO₄ (B) kristallisiert in der Raumgruppe I4_lmd (No. 109) mitZ=4,a=7,417 (1) undc=16,610 (2) Å. Die Cr–F- und Cr–N-Abstände sind 1,894 (3); 2,087 (6), 2,083 (5) Å für A und 1,887 (6); 2,062 (5), 2,051 (7) Å für B. Die octaedrischen Bindungswinkel innerhalb der Kationen weichen nicht viel von 90° ab. Der Cr–N-Abstand intrans-Position der Cr–F-Bindung ist kürzer. Die Strukturen wurden bis zu GütefaktorenR ₂ 0,072 (A) und 0,058 (B) verfeinert. Bei der Verbindung A wurden schwache N–H ... F-Wasserstoff-Bindungen zwischen verschiedenen Kationen beobachtet, während bei der Verbindung B keine Wasserstoff-Bindungen vorhanden sind.

     

Synthesis and crystal structures of two new zigzag versus helical coordination polymers based on diphenic acid

Two new coordination polymers, [Mn(dpa)(2,2′-bipy)] _n (1) and [Ni(dpa)(2,2′-bipy)] _n (2) (H₂dpa = 3,4′-biphenyl-dicarboxylic acid, 2,2′-bipy = bipyridine), have been synthesized and structurally characterized by elemental analysis, IR, and X-ray diffraction. Single-crystal X-ray analyses revealed that 3,4′-diphenic acid acts as a bridging ligand, exhibiting rich coordination modes to link metal ions: μ ₂–η ¹: η ¹, μ ₁–η ¹: η ¹, and μ ₁ –η ¹: η ⁰. Compound 1 demonstrates a 1-D zigzag chain. Compound 2 is a 1-D helical chain. In 1 and 2, there exist intermolecular π–π stacking interactions and non-covalent interactions responsible for the stabilization of the supramolecular structure. In 1, the Mn(II) chains exhibit a weak antiferromagnetic interaction.     

Three new pyridine-2,6-dicarboxylate copper(II) compounds with coordinated pyridine-based ligands: Synthesis, characterisation and crystal structures

Three new Cu(II) compounds of pyridine-2,6-dicarboxylic acid (H₂pdc) with meta-substituted pyridines as additional ligands have been synthesized and structurally characterised using X-ray diffraction. Two of them are mononuclear compounds, i.e. [Cu(pdc)(3acpyr)(H₂O)] (1) (3acpyr = 3-acetylpyridine) and [Cu(pdc)(3HOp)(H₂O)](H₂O)₂ (2) (3HOp = 3-hydroxypyridine). The third compound is polynuclear, i.e. [Cu(pdc)(μ-3HOmp-κN,O)]_n (3) (3HOmp = 3-(hydroxymethyl)pyridine). The three compounds are also characterised by IR, EPR and ligand field spectroscopy. The geometry around the Cu(II) ions is distorted square pyramidal for compounds 1 and 2 and distorted octahedral for compound 3. The lattice of compound 1 is organised by an intra-sheet hydrogen-bond pattern generating double layers. Compound 2 has a lattice arranged by the two water molecules in the lattice with complicated 2D O-H?O intra-sheet hydrogen bonding motifs.The zig-zag chains in compound 3 are further organised in layers, due to the axial coordination at Cu(II), forming a so-called (4, 3) ladder-like one-dimensional coordination polymer. These ladders are interconnected by hydrogen bonding.     

Syntheses,crystal structures,and catalytic activities of three new Cu(II) coordination polymers based on 2-(1H-1,2,4-triazole)-1-acetic acid

Three new coordination polymers, {[Cu(trza)(2,2′-bipy)(H₂O)]?·?(ClO₄)} _n (1), {[Cu(trza)(2,2′-bipy)(H₂O)]?·?(BF₄)} _n (2), and {[Cu(trza)(4,4′-bipy)]?·?(H₂O)?·?(ClO₄)} _n (3) (Htrza?=?2-(1H-1,2,4-triazole)-1-acetic acid), have been synthesized and characterized by single-crystal X-ray diffraction analysis. Both 1 and 2 exhibit 1-D chain structure while 3 displays 2-D layer structure. The catalytic activities of 1 and 3 in the green oxidative coupling of 2,6-dimethylphenol have been investigated.     

Synthesis,structures and photoluminescence of two Er(III) coordination polymers

Two new erbium compounds, [Er₂(BDC)₃(DMF)₂] (1) and [Er₂(CQC)₃(DMF)₃(H₂O)]?·?DMF?·?H₂O (2), where BDC stands for 1,4-benzenedicarboxylate, CQC for 2-(4-carboxyquinolin-2-yl)quinoline-4-carboxylate, and DMF for N,N-dimethylformamide, have been synthesized through pre-heating and cooling-down crystallization. In 1 the Er(III) is seven-coordinate with oxygen atoms from six BDC and one DMF, forming a three-dimensional open-framework structure. Compound 2 possesses a 2D structure based on dinuclear Er(III) building units. The photoluminescence of 1 has also been investigated.     

pH-controlled assembly of two new supramolecular hybrid compounds based on Keggin polyoxotungstates

Two supramolecular compounds based on Keggin polyoxotungstates, (4,4′-H₂bpy){[Cu(4,4′-bpy)]₂[SiW₁₂O₄₀]} (1) and (4,4′-H₂bpy)₂[SiW₁₂O₄₀]·2H₂O (2) have been synthesized and characterized by elemental analyses, IR, UV, XPS spectra, TG analyses, and single crystal X-ray diffraction analyses. Compound 1 exhibits an infinite 1-D ladder like structure, which is further interconnected into a 3-D supramolecular framework via hydrogen bonding interactions. Compound 2 contains 4,4′-bipyridine (4,4′-bpy), pseudo-Keggin polyoxoanions [SiW₁₂O₄₀]^4?, and water molecules. Polyoxoanions together with water molecules in 2 construct a 3-D inorganic supramolecular network through O···O and O···Ow(1) interactions. The electrochemical behaviors and photocatalytic properties of 1 and 2 have been investigated.     

Crystal structures and antibacterial activities of two enoxacin based compounds

Hydrothermal reactions of Cu(ClO₄)₂ · 6H₂O and Cu(SO₄)₂ · 5H₂O with enoxacin yielded two compounds, (H₂-Eno) · ClO₄ (1) and [Cu(H-Eno) · (H₂O)₂ · SO₄] · 2H₂O (2). Their solid-state structures have been characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction analyses. Compounds 1 and 2 were screened for antibacterial activity against Staphylococcus aureas, Escherichia coli, Pseudomonas aeruginos and Candida albicans.     

Synthesis and properties of azole-substituted ferrocenes

4-Ferrocenyltriazole, 4-(4-ferrocenylphenyl)triazole, 4-ferrocenyltetrazole, and 4-(4-ferrocenylphenyl)tetrazole have been prepared. Redox potentials and decomposition temperatures were evaluated and all the compounds were crystallographically characterized; in most cases, weak intermolecular CH?N hydrogen bonds (H?N dist. = 2.3-2.5 Å) were formed between the azole moieties. Two polymorphs were found for 4-ferrocenyltetrazole, formed with either CH?N or π-π interactions.     

Syntheses,structures, and luminescence of coordination compounds based on N-containing polycarboxylates

Six coordination compounds constructed by two structurally related flexible nitrogen-containing polycarboxylate ligands 2,2′-(2,2′-(ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(methylene)bis(azanediyl)dibenzoic acid (H₂L1) and 5,5′-(2,2′-(ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(methylene)bis(azanediyl)diisophthalic acid (H₄L2) have been synthesized: [Ni(H₂O)₆]?·?L1?·?(C₂H₅OH)_0.5?·?H₂O (1), [Co(L1)(L3)]?·?CH₃OH (2), [Ni(L1)(L3)]?·?CH₃OH (3), [Zn(L1)(L3)]?·?CH₃OH (4), [Cd(L1)(L3)]?·?CH₃OH (5), and [Zn(L2)_0.5(phen)]?·?C₂H₅OH (6), where L3?=?3,4?:?9,10?:?17,18?:?23,24-tetrabenzo-1,12,15,26-tetraaza-5,8,19,22-tetraoxacyclooctacosan and phen?=?1,10-phenanthroline. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 displays a discrete structure, which is further linked by hydrogen bonds to form a 2-D supramolecular layer. Compounds 2–5 display similar structures. These compounds possess 1-D meso-chain structures linked by L1 and metals. The C–H?···?π interactions from neighboring chains extend the chains in different directions, giving a 3-D plywood network. Compound 6 possesses 2-D layers, which are further linked by hydrogen-bonding interactions to generate a 3-D supramolecular architecture.