Kittipong Chainok

Copper(II) complex as a precursor for formation of cyano-bridged pentanuclear FeIII-CuII bimetallic assembly: Synthesis, characterization, crystal structure and antibacterial activity

Abstract[CuL(ClO4)2] (1) (L = 3,10-diisobutyl-1,3,5,8,10,12-hexaazacyclotetradecane) was synthesized by condensation reaction of ethylenediamine, formaldehyde and iso-butylamine in absolute ethanol. Characterization of 1 utilized various spectroscopic techniques, viz. elemental analysis, electrospray ionization-mass spectrometry (ESI-MS), Fourier-transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-Vis), diffuse reflectance spectroscopy (DRS) and thermogravimetric analysis (TGA). Based on these techniques, the structure of 1 was proposed as Cu(II) ion occupying octahedral geometry with four secondary amine nitrogens of the hexaazamacrocyclic ligand and two perchlorato anions. 1 was used as a precursor in the preparation of cyano-bridged bimetallic compound, [CuL]3[Fe(CN)6]2⋅5H2O (2), by reaction with K3[Fe(CN)6] in aqueous solution. Single-crystal X-ray analysis indicated that 2 crystallized in the monoclinic system with space group P21/n. The structure of 2 consisted of cyano-bridged FeIII-Cu II pentanuclear molecules having two [Fe(CN)6] 3− anions connected to three cis-[CuL] 2+ cations via two cis-cyanide ligands from each ferrate unit. In each of pentanuclear unit, the central [CuL] 2+ cation exhibited a distorted octahedral geometry while the other two units exhibited a distorted square pyramidal geometry. The room temperature magnetic moments of both complexes were measured to be 1.92 B.M. for 1 and 5.61 B.M. for 2. The in vitro antibacterial activity of 1 against Staphylococcus aureus ATCC 25923, Escherichia coli ATCC 25922, and Pseudomonas aeruginosa ATCC 27853 strains were studied and compared with standard drugs, which showed moderate antibacterial activity compared with Penicillin and Gentamicin. Graphical AbstractA copper mononuclear complex was synthesized, characterized with various techniques, and used as a precursor to synthesize a pentanuclear (FeIII-CuII) complex. The Xray structure of the new pentanuclear complex is reported. The precursor copper complex exhibited moderate antibacterial activity.

Crystal structures of (E)-N′-(2-hy­droxy-5-methyl­benzyl­idene)isonicotinohydrazide and (E)-N′-(5-fluoro-2-hy­droxy­benzyl­idene)isonicotinohydrazide

The title isonicotinohydrazides adopt an E conformation about the C=N bonds and in each molecule there is an intramolecular O—H⋯N hydrogen bond, forming an S(6) ring motif. In the crystals of both compounds, zigzag chains are formed via N—H⋯N hydrogen bonds, in the [10] the first compound and [010] for the other.

Crystal structure of poly[(2,2′-bi­pyridine-κ2N,N′)tetra-μ2-cyanido-κ4C:N;κ4N:C-manganese(II)disilver(I)]

The title compound, [Ag2Mn(CN)4(C10H8N2)]n or Mn(bipy){Ag(CN)2}2 (bipy = 2,2′-bipyridine) is isostructural with Cd(bipy){Au(CN)2}2 [Guo et al. (2009 ▸). CrystEngComm, 11, 61–66]. The MnII atom has crystallographically imposed twofold symmetry and a distorted octahedral coordination sphere consisting of six N atoms from one bipyridine ligand and four dicyanoargentate(I) anions, [Ag(CN)2]−, while the AgI atom of the complex anion displays the expected linear geometry. Each [Ag(CN)2]− unit connects to two neighbouring [Mn(bipy)]2+ cations to give an threefold interpenetrating quartz-like three-dimensional framework. No directional interactions beyond van der Waals contacts are observed.

Synthesis of Encapsulated Zn(8-hydroxyquinoline)2(H2O)2 in the Pore of BioMOF1 for Sensing Dissolved Oxygen in Water

The Zn(8-hydroxyquinoline)2(H2O)2, ZnQ2·2H2O, encapsulated in the porous BioMOF1 (ZnQ2@BioMOF1) host was synthesized by solid-solid and solid-solution reaction between Zn2+@BioMOF1 and 8-hydroxyquinoline. To prepare Zn2+@BioMOF1, dimethylammonium (DMA+), guests in the pores of BioMOF1 were replaced by Zn2+ ions via ion exchange process. The synthesized compound was characterized by XRD and TGA to confirm stability of BioMOF1 host. The ZnQ2·2H2O forming by metal-cation-directed de novo coassembly approach was confirmed by UV, IR, Fluorescence, BET, and confocal microscopy. Scanning electron microscopy images show slight change in morphology of BioMOF1 after introducing ZnQ2·2H2O by solid-solution reaction into its pores. Thin films of the produced materials were used to sense dissolved oxygen in water by using fluorescence technique.

Temperature dependent 3D structures of lanthanide coordination polymers based on dicarboxylate mixed ligands

Fourteen three-dimensional (3D) lanthanide coordination polymers (CPs) with dicarboxylate mixed ligands, [Ln(fum)1.5(H2O)2]·0.5(H2bdc)·H2O (Ln = Sm (1), Tb (2)), [Ln2(fum)2(bdc)(H2O)4]·2H2O (Ln = Sm (3), Eu (4), Tb (5), Er (6)), [Ln(fum)0.5(bdc)] (Ln = Sm (7), Eu (8), Tb (9), Er (10)), and [Ln2(bdc)2(ox)(H2O)4]·0.7H2O (Ln = Sm (11), Gd (12), Tb (13), Dy (14)), have been synthesized hydrothermally from the self-assembly of lanthanide(III) ions (Ln3+), fumaric acid (H2fum), and terephthalic acid (H2bdc) in the presence of potassium hydroxide at different temperatures. The compounds fall into four classes. Compounds 1 and 2 were isolated from hydrothermal reactions performed at a relatively low temperature of 100 °C and found to crystallize in the triclinic space group P. The 3D framework is assembled from 2D layers of [Ln(fum)(H2O)2] units pillared by the chelating fum ligands and has 1D rhombic channels templated by H2bdc and lattice H2O molecules. The framework presents a binodal (4,5)-connected tcs topology with the point symbol (44·62)(44·66). Raising the reaction temperature to 140 °C resulted in the formation of compounds 3–6. These materials crystallize in the monoclinic system with the polar space group P21 and feature a 3D network constructed from dinuclear {Ln2(OCO)6(H2O)4} units interlinked by fum and bdc ligands, showing a uninodal 6-connected two-fold interpenetrated pcu topology. The small channels of the framework are occupied by lattice H2O molecules. Further increase of the reaction temperature to 160 °C gave rise to the formation of compounds 7–10, crystallizing in the orthorhombic space group Pbca. The 3D framework is generated from 2D corrugated sheets of [Ln(fum)]2+ bound by bdc ligands and contains no intercalated H2O molecules in the lattice. The framework possesses a trinodal (4,6,7)-connected net with the point symbol (42·64)2(46·68·8)(412·69)2. Finally, compounds 11–14 contained an in situ generated oxalate (ox) ligand formed under hydrothermal conditions conducted at a high reaction temperature of 180 °C. These compounds crystallize in the monoclinic space group P21/c and possess a 3D open framework consisting of a dinuclear [Ln2(ox)(H2O)4]2+ unit linked by bridging bdc ligands and has small void channels occupied by lattice H2O molecules. The frameworks were topologically simplified as a binodal (4,5)-connected tcj/hc net with a total point symbol of (42·52·72)(42·53·75). In the solid state at room temperature, the Tb (2, 5, 9, and 13) and Eu (4 and 8) compounds emit green and red light, respectively.

Crystal structure of (E)-N′-(3-fluoro-2-hy­droxy­benzyl­idene)isonicotinohydrazide

The title isonicotinohydrazide derivative is planar, with an r.m.s. deviation for the fitted non-H atoms of 0.062 Å, and an intramolecular O—H⋯N hydrogen bond with an S(6) ring motif. In the crystal, molecules are linked by N—H⋯N and C—H⋯N hydrogen bonds forming chains propagating along the a-axis direction.

Crystal structure of poly[di­aqua­bis­(μ5-benzene-1,3-di­carboxyl­ato)(N,N-di­methyl­formamide)­cadmium(II)disodium(I)]

A novel three-dimensional bimetallic CdII–NaI metal–organic framework has been synthesized and the X-ray structure has been reported.

Crystal structures of tetra­methyl­ammonium (2,2′-bi­pyridine)­tetra­cyanidoferrate(III) trihydrate and poly[[(2,2′-bi­pyridine-κ2N,N′)di-μ2-cyanido-dicyanido(μ-ethyl­enedi­amine)(ethyl­enedi­amine-κ2N,N′)­cadmium(II)iron(II)] monohydrate]

The cyanide complex [N(CH3)4][Fe(2,2′-bipy)(CN)4]·3H2O (2,2′-bipy is 2,2′-bipyridine) was synthesized as a building block for the construction of a new two-dimensional cyanide-bridged Fe–Cd bimetallic coordination polymer, [Fe(2,2′-bipy)(CN4)Cd(en)2]·H2O, in which ethylenediamine (en) adopts both bridging and chelating coordination modes.

A novel one-dimensional double-chain-like ZnII coordination polymer: poly[bis­(1-benzyl-1H-imidazole-κN3)tris­(μ-cyanido-κ2C:N)(cyanido-κC)disilver(I)zinc(II)]

One of most interesting systems of coordination polymers constructed from the first-row transition metals is the porous ZnII coordination polymer system, but the numbers of such polymers containing N-donor linkers are still limited. The title double-chain-like ZnII coordination polymer, [Ag2Zn(CN)4(C10H10N2)2]n, presents a one-dimensional linear coordination polymer structure in which ZnII ions are linked by bridging anionic dicyanidoargentate(I) units along the crystallographic b axis and each ZnII ion is additionally coordinated by a terminal dicyanidoargentate(I) unit and two terminal 1-benzyl-1H-imidazole (BZI) ligands, giving a five-coordinated ZnII ion. Interestingly, there are strong intermolecular AgI...AgI interactions between terminal and bridging dicyanidoargentate(I) units and C-H...π interactions between the phenyl rings of BZI ligands of adjacent one-dimensional linear chains, providing a one-dimensional linear double-chain-like structure. The supramolecular three-dimensional framework is stabilized by C-H...π interactions between the phenyl rings of BZI ligands and by AgI...AgI interactions between adjacent double chains. The photoluminescence properties have been studied.

Crystal structure of 4-nitro-N-[(pyridin-2-yl)methyl­idene]aniline

The title compound, C12H9N3O2, adopts an E conformation at the imine double bond. The pyridyl ring makes a dihedral angle of 47.78 (5)° with the benzene ring, indicating the molecule is twisted. In the crystal, molecules are π–π stacked into columns parallel to [100], with an interplanar separation of 3.8537 (8) Å, corresponding to the length of the a axis. The chains are further linked via weak C—H⋯O and C—H⋯N hydrogen bonds, forming two-dimensional sheets parallel to (010). The sheets interact by van der Waals interactions.