Supramolecular inclusion of a pillared double-layered host by an anion-directed second-sphere coordination

In this paper, we have illustrated the utilisation of a second-sphere coordination approach to construct supramolecular inclusion solids with varieties of guest molecules. A flexible molecule N,N,N′,N′-tetra-p-methylbenzyl-ethylenediamine (L1) bearing doubly protonated H-bond donors was designed, capable of forming N–H…Cl hydrogen bonds with a crystallographically unique chloride anion, to construct an anion-directed ligand. The pillared double-layered host framework was constructed by an anion-directed ligand and primary coordination sphere [CoCl₄]^2 ?  through weak C–H…Cl hydrogen-bonding interactions. A variety of guest molecules, such as p-anisaldehyde, 1,4-dimethoxy-2,5-bis(methoxymethyl)benzene, can be included, leading to the formation of novel supramolecular inclusion solids: [L1]·4[H]⁺·[CoCl₄]^2 ? ·2Cl^? ·1.5[C₈H₈O₂]·0.25[CH₃OH] (1) and [L1]·4[H]⁺·[CoCl₄]^2 ? ·2Cl^? ·1.5[C₁₂H₂₀O₄]·0.5[CH₃OH] (2).

We have presented herein the utilisation of a second-sphere coordination approach to construct supramolecular inclusion solids with a variety of guest molecules. A novel type of a pillared double-layered host framework was constructed by a second-sphere coordination between the anion-directed ligand (L1 = N,N,N′,N′-tetra-p-methylbenzyl-ethylenediamine) and [CoCl₄]^2 ?  through weak C–H…Cl hydrogen-bonding interaction, and a variety of guest molecules, such as p-anisaldehyde, 1,4-dimethoxy-2,5-bis(methoxymethyl)benzene, can be included, leading to the formation of supramolecular inclusion solids: [L1]·4[H]⁺·[CoCl₄]^2 ? ·2Cl^? ·1.5[C₈H₈O₂]·0.25[CH₃OH] (1) and [L1]·4[H]⁺·[CoCl₄]^2 ? ·2Cl^? ·1.5[C₁₂H₂₀O₄]·0.5[CH₃OH] (2)

     

Syntheses,weak interactions,and 3-D network structures of two salts based on [Ni(i-mnt)2]2− (i-mnt2−=iso-maleonitriled-ithiolate) anion with substituted pyridinium cation

Two new salts, [2-NaMePy]₂[Ni(i-mnt)₂] (1) and [2-NaMe-4-MePy]₂[Ni(i-mnt)₂] (2) ([2-NaMePy]⁺ = 1-(2′-naphthylmethyl)pyridinium, [2-NaMe-4-MePy]⁺ = 1-(2′-naphthylmethyl)-4-methylpyridinium and i-mnt^2? = iso-maleonitriledithiolate), have been prepared and characterized by elemental analyses, UV, IR, molar conductivity, and single crystal X-ray diffraction. The anions in 1 form a 1-D chain through short C ··· N interactions between the anions, while the cations in 2 stack a 1-D column via C–H ··· π and π ··· π stacking interactions between the cations. The effect of weak intramolecular interactions such as C–H ··· N, C–H ··· S, C–H ··· Ni hydrogen bonds, and π ··· π stacking interactions between the cations and the anions further generate a 3-D network structure. The change of the molecular topology of the countercation when the 4-substituted group in the pyridine ring is changed from H atom to CH₃ group results in different crystal system, space group, and the stacking mode of the cations and anions of 1 and 2.     

Haloalkane adsorption into 1-D ensembles’ channels: Zn(II) coordination polymers

Abstract

Self-assembly of ZnX₂ (X^–?=?Cl^–, Br^–, and I^–) with 2,7-bis(isonicotinoyloxy)naphthalene (L) in a mixture of ethanol and dichloromethane yields 1-D zigzag chains of [ZnX₂L·2CH₂Cl₂]_n composition. The 1-D chains form an ensemble constituting hydrophobic suprachannels of 4.0–4.4?×?4.4–5.0 Ų with repeat units of ZnL for [ZnCl₂L] and [ZnBr₂L], and those of 5.2?×?12.0 Ų with repeat units of Zn₂L₂ for [ZnI₂L] in the appropriate arrays via C–H···π and π···π interactions. The most interesting feature is that alcohol molecules are not incorporated into the haloalkane-philic channels. That is, the channels discriminate haloalkanes from alcohols. Furthermore, the exchange of solvate molecules in a crystalline state indicates that the unique channels show different absorptions of haloalkanes such as CH₂Cl₂, CH₂Br₂, CH₂I₂, CHCl₃, 1,2-dichloroethane, and 1,2-dibromoethane.     

Bis(N‐acetyltriethylphosphaniminium)‐tetraacetato‐dichloro‐dicuprat(II), [MeC(O)N(H)PEt3]2[Cu2(O2C–Me)4Cl2]

Bis(N‐acetyltriethylphosphaneiminium)‐tetraacetato‐dichloro‐dicuprate(II), [MeC(O)N(H)PEt₃]₂[Cu₂(O₂C–Me)₄Cl₂] The title compound has been prepared by the reaction of Me₃SiNPEt₃ with [Cu₂(O₂C–Me)₄] and MeC(O)Cl in dichloromethane solution to give colourless crystals which include four molecules CH₂Cl₂ per formula unit. The complex is characterized by IR spectroscopy and by a crystal structure determination. [MeC(O)N(H)PEt₃]₂[Cu₂(O₂C–Me)₄Cl₂] · 4 CH₂Cl₂: Space group P2₁/n, Z = 2, lattice dimensions at –70 °C: a = 794.1(1), b = 2356.9(6), c = 1327.3(2) pm; β = 91.00(1)°; R₁ = 0.0597. The structure consists of N‐acetyltriethylphosphaneiminium cations and dianions [Cu₂(O₂C–Me)₄Cl₂]^2– which form an iontriple with N–H…Cl hydrogen bridges.     

Die Bromokomplexe von Molybdän(IV) [MoBr6]2⊖ und [Mo2Br10]2⊖. Die Kristallstruktur von (PPh3Me)2[MoBr6] · 2 CH2Br2

Bromo Complexes of Molybdenum(IV) [MoBr₆]^2? and [Mo₂Br₁₀]^2?. Crystal Structure of (PPh₃Me)₂[MoBr₆] · 2 CH₂Br₂ The bromomolybdates(IV) (PPh₃Me)₂[MoBr₆] · 2 CH₂Br₂ and (PPh₄)₂[Mo₂Br₁₀] are obtained by reactions of molybdenum tetrabromide with PPh₃MeBr and PPh₄Br, respectively. They form black-brown, hydrolysis sensitive crystal powders. The crystal structure of (PPh₃Me)₂[MoBr₆] · 2 CH₂Br₂ was determined by X-ray diffraction (2376 independent observed reflexions, R = 0.082). Crystal data: a = 1024, b = 1131, c = 1179 pm, α = 108.2°, β = 106.8°, γ = 99.0°, space group P1 , Z = 1. The compound consists of PPh₃Me⁺ ions, CH₂Br₂ molecules and nearly octahedral [MoBr₆]^2? ions with MoBr bond lengths between 252.7 and 254.0 pm.     

The rigid isomeric 5-(x-pyridyl)-1H-tetrazole ligands-directed various isopolymolybdate-based compounds: assembly,structures, and properties

Two new isopolymolybdate-based metal–organic complexes, [Cu₂(2-ptz)₂(Mo₄O₁₄)_0.5] (1) and [Cu₃(OH)₂(3-ptz)₄(γ-H₄Mo₈O₂₆)(H₂O)₄]·10H₂O (2) (2-ptzH = 5-(2-pyridyl)-1H-tetrazole, 3-ptzH = 5-(3-pyridyl)-1H-tetrazole), constructed from isomeric ligands with different N-donor sites were synthesized under hydrothermal conditions. In 1, each [Mo₄O₁₄]^4? cluster connected with six neighboring [Mo₄O₁₄]^4? clusters through six binuclear [Cu₂(2-ptz)₂]²⁺ subunits to yield a 2-D layer. In 2, bidentate inorganic [Mo₈O₂₆]^4? anions link the trinuclear [Cu₃(OH)₂(3-ptz)₄] clusters to construct a 1-D chain. Adjacent chains connect through Mo–N bonds between the [Mo₈O₂₆]^4? anions and pyridyl groups from the trinuclear clusters to form a 2-D layer. The effect of the N-donor sites of the rigid isomeric ligands on the structures of 1 and 2 was discussed. The electrochemical properties and photocatalytic activities of 1 and 2 have also been studied.     

Layered structures constructed by second-sphere coordination via N–H ··· Cl and C–H ··· Cl hydrogen bonding: synthesis and crystal structures of tribenzylamine and [MCl6] (M = Sn,Re, and Te)

A series of second-sphere coordination complexes of tribenzylamine (L ¹ ) and [MCl₆] (M = Sn, Re, Te) have been synthesized and characterized by spectroscopic techniques (IR, NMR) and single-crystal X-ray diffraction. The main driving force for the encapsulation of [MCl₆] and recognition with L ¹ is the second-sphere coordination of metal halides by the amide protons of the ligand via hydrogen bonding (N–H ··· Cl–M and C–H ··· Cl–M); new layered structures are described. Thermal stability and irreversible behavior of second-sphere coordination complexes [L ² ] · 0.5[TeCl₆]^2? · HCl · (H₃O)⁺ · 0.5H₂O (L ² = N,N,N′,N′-tetrabenzyl-ethylenediamine) in contact with water vapor are also described.     

{[Cu2Br3]n [Cu(H-Leof)2]·2H2O}(Leof是左氟沙星)(英)

C om m ent Levofloxacin (S-(-)9-fluoro-2,3-dihydro-3-m ethyl- 10-(4-m ethyl-1-piperazinyl)-7-oxo-7H -pyrido[1,2,3-de]- 1,4-benzoxaxin-6-carboxilic acid)(Leof),is a synthetic fluorinated quinolone derivative, having activity a- gainstboth Gram ( )and Gram …     

Ternary copper(II) complexes of aroylhydrazones and mono/bidentate heterocycles with different structures: synthesis,crystal structure and properties

Two mixed-ligand Cu(II) complexes, [CuL¹(Himdz] · CH₃OH (1) and [CuL²(phen)] · 0.5DMF (2), with different structures have been synthesized by using substituted aroylhydrazones, 5-bromo-salicylaldehyde-benzoylhydrazone (H₂L¹) and 5-bromo-salicylaldehyde-3,5-dimethoxy-benzoylhydrazone (H₂L²), and mono/bidentate heterocycles, imidazole (Himdz) and 1,10-phenanthroline (phen). Their crystal structures and spectroscopic properties have been studied. X-ray analysis show a distorted square-planar geometry for 1 and a distorted square-pyramidal geometry for 2, in which the chelating phen ligand displays axial-equatorial bonding. In both structures the ONO tridentate ligand occupies the basal plane. Self-assembly via O–H ··· N, N–H ··· O and C–H ··· O interactions lead to one-dimensional chain arrangement in 1 and 2.     

Structure and inclusion property of supramolecular host framework [H2 L1][XCl4], L1 = N,N,N′,N′-tetra-p-methoxybenzyl-ethylenediamine; X = Fe, Co, Pd

In this paper, we have used the hydrogen-bonding interactions, combining the designed diamine ligands and anionic metal chlorides, into the construction of a series of new pillar-layered supramolecular complexes. The flexible molecule N,N,N′,N′-tetra-p-methoxybenzyl-ethylenediamine (L1) bearing doubly protonated H-bond donors, has been synthesized and reacted with the metal chlorides (such as [PdCl₄]^2?, [FeCl₄]^? and [CoCl₄]^2?) via weak C–H···Cl interactions, yielding crystal products [H₂ L1]²⁺·Cl^?·[FeCl₄]^? (1), 0.5H₂O ? [H₂ L1]²⁺·Cl^?·0.5[PdCl₄]^2? (2) and [2-hydroxy naphthyl]_1.5 ? 2[H₂ L1]²⁺·2Cl^?·[CoCl₄]^2? (3). The 3-D networks are organic double layers formed by the self-assembly of the ligands through extensive hydrogen-bonding interactions (C–H···O or C–H···π interactions) and further interconnected by [PdCl₄]^2?/[FeCl₄]^?/[CoCl₄]^2? in a pillar fashion, constructing into pillar-layered networks with channels accessible to various guest molecules. The inclusion property of [H₂ L1][CoCl₄] was studied, varieties of guest molecules, such as 2-hydroxy naphthyl, phenanthrene and hydroquinone, can be included in the framework.     

Inclusion of Cl− or Br− anions within host framework formed by second-sphere interactions

In this study, we have deliberately utilized the second-sphere coordination approach into the construction of supramolecular inclusion solids Cl ? [H₂ L1]·[InCl₄] (Crystal I) and Br ? [H₂ L1]·[TeBr₆] (Crystal II). The chloride or bromine anions can be encapsulated inside the host assemblies formed by the diamine molecule (4,6-dimethyl-1,3-phenylene) bis(N,N-dibenzylmethane) (L1) and the metal complexes ([InCl₄]^? and [TeBr₆]^2?) via second-sphere interactions. The inclusion complexes have been structurally characterized by X-ray crystallography, indicating that weak C–H···Cl and C–H···Br hydrogen bonding synthons play a significant role in the construction of host framework. 2-D networks are formed in both complexes by the interconnection of 1-D networks through the multiple weak hydrogen bonding interactions with [InCl₄]^? or [TeBr₆]^2?. The guest Cl^? or Br^? anions are encapsulated inside the host cages through N–H···Cl hydrogen bonds. The inclusion selectively was studied for the two host assemblies.     

Preparations,IR spectra and crystal structures of cyano-bridged bimetallic complexes of zinc(II) and cadmium(II) with tetracyanopalladate(II)

The novel heteronuclear compounds [Zn(hydet-en)₂Pd(CN)₄] (1) and [Cd(hydet-en)₂Pd(CN)₄] (2) {hydet-en: N-(2-hydroxyethyl-ethylenediamine)} have been synthesized and characterized by elemental analyses and IR spectra. The crystal structures of 1 and 2 have been determined by X-ray diffraction. Structural analysis shows that both compounds have shown a polymeric chain, in which the Zn(II)/Pd(II) and Cd(II)/Pd(II) centres are linked by two CN groups. Both zinc and cadmium atoms are six coordinate with two trans cyanide–nitrogen and four hydet-en N atoms in a distorted octahedron arrangement; the palladium atoms in 1 and 2 are four coordinate with four cyanide-C atoms in a square planar arrangement. The chains in both compounds are connected through weak interchain hydrogen bonds, N–H?···?O, N–H?···?N and O–H?···?N, thereby forming a three-dimensional network.     

Self-assembly of copper(II) complexes with substituted aroylhydrazones and monodentate N-heterocycles: synthesis,structure and properties

Two ternary copper(II) complexes [Cu(L¹)(py)] (1) and [Cu(L²)(Himdz]?·?CH₃OH (2) with substituted aroylhydrazones, 5-bromo-salicylaldehyde-3,5-dimethoxy-benzoylhydrazone (H₂L¹) and 5-bromo-salicylaldehyde-p-methyl-benzoylhydrazone (H₂L²), pyridine (py) and imidazole (Himdz), have been synthesized. Their crystal structures and spectroscopic properties have been studied. In each complex, the metal is in a square-planar N₂O₂ coordination formed by the phenolate-O, the imine-N and the deprotonated amide-O atoms of L^2?, and the sp²?N atom of the neutral heterocycle. In the solid state, 1 exists as a centrosymmetric dimer due to very weak apical coordination of the metal bound phenolate-O. Complex 2 has no such apical coordination and exists as a monomer. Self-assembly via C–H?···?O, N–H?···?O and O–H?···?N interaction leads to a one-dimensional chain arrangement; other non-covalent interactions such as C–H?···?π and π?···?π are not involved.     

The assembly of POM-induced inorganic–organic hybrids based on copper ions and mixed ligands

Three inorganic–organic hybrid materials based on Keggin-type polyoxometalates (POMs), [Cu^II₂(phen)₂(4,4′-bipy)(H4,4′-bipy)₂(H₂O)₂][PMo₁₂O₄₀]₂·2H₂O (1), [Cu^II(phen)₂(H4,4′bipy)][PW₁₂O₄₀]·H₂O (2), and [Cu^II₂(phen)₂(4,4′-bipy)(BW₁₂O₄₀)(H₂O)₂](H₂4,4′-bipy)_0.5·3H₂O (3) (phen = 1,10-phenanthroline, 4,4′-bipy = 4,4′-bipyridine), were synthesized using different POMs in the hydrothermal conditions. Compounds 1–3 were characterized by single-crystal X-ray diffraction, IR spectra, elemental analyses, powder X-ray diffraction analyses, and thermogravimetric analyses. Compound 1 presents a two-dimensional (2-D) network containing the Keggin-type [PMo₁₂O₄₀]^3? anion and dinuclear metal–organic units [Cu^II₂(phen)₂(4,4′-bipy)(H4,4′-bipy)₂(H₂O)₂]³⁺. Compound 2 is a 2-D architecture constructed from a [PW₁₂O₄₀]^3? and mononuclear metal–organic units [Cu^II(phen)₂(H4,4′-bipy)]³⁺. In 3, the [BW₁₂O₄₀]^5? anions link [Cu^II₂(phen)₂(4,4′-bipy)] units to form a one-dimensional (1-D) chain [Cu^II₂(phen)₂(4,4′-bipy)(BW₁₂O₄₀)(H₂O)₂]; the 1-D chain connects with protonated 4,4′-bipy ligands and lattice waters, yielding a 2-D layer. Fluorescence spectra, UV–vis spectra, and electrochemical properties of 1–3 have been investigated.     

Tetrakis­(diethyl­amino)­phospho­nium bromide hemihydrate

The structure of the title compound, C₁₆H₄₀N₄P⁺·Br^?·0.5H₂O or [P{N(C₂H₅)₂}₄]Br·0.5H₂O, at 130 K has Z′ = 4 and is ionic, with Br not bonded to P. The P atoms are tetrahedral, with P—N distances in the range 1.628 (2)–1.6400 (19) Å. The N atoms are approximately planar. The water mol­ecules form cyclic hydrogen‐bonded [(H₂O)₂Br₂]^2? units about inversion centers, with O?Br distances in the range 3.425 (2)–3.611 (3) Å.     

Syntheses,crystal structures and photophysical properties of d10 transition-metal (Ag+, Cu+, Cd2+ and Zn2+) coordination complexes based on a thiophene-containing heterocyclic thioamide

Four d¹⁰ transition-metal coordination complexes 1–4 (1: [Ag₂(TPT)₂(TPTH)₂]; 2: [Cu₆(TPT)₆]·2DMF; 3: [Cd(TPT)₂(TPTH)]·CH₃CH₂OH, 4: [Zn(TPT)₂]_n) have been constructed from a newly designed heterocyclic thioamide ligand, TPTH (TPTH = 4-(thiophen-2-yl)-pyrimidine-2-thiol). All complexes have been structurally elucidated by single crystal X-ray diffraction analyses. Except for 4, which shows a one-dimensional (1-D) chain structure, 1–3 are all discrete coordination complexes featuring dinuclear, hexanuclear and mononuclear entities, respectively. Their photophysical properties have been evaluated in the solid state at room temperature by UV–vis diffuse reflectance and luminescence spectra. Among them, 2 exhibits a strong red luminescence (λ_em = 699 nm) with a remarkable red-shift of the maximum emission compared to that of the TPTH ligand (λ_em = 536 nm). The red emission observed with 2 is ascribed to a LMCT (ligand-to-metal charge transfer) transition which agrees with the DFT calculations.     

Metal complexes of indole-3-acetic acid: synthesis,crystal structures,and Pb2+ chemosensing by cation-exchange reaction

Two binuclear complexes [Cu₂(IA)₄(DMSO)₂]·CH₃OH (1), [Cd₂(IA)₂(phen)₂I₂] (2), and one 1-D {[Pb₂(IA)₄]·CH₃OH}_n (3) (IAH = indole-3-acetic acid, phen = 1,10-phenanthroline) have been prepared and characterized by single crystal X-ray diffraction. Both 1 and 2 are binuclear wherein the central Cu ions are bridged by IA in 1, while Cd ions are bridged by I^? in 2. Complex 3 has a 1-D chain structure based on secondary building units (SBUs) of [Pb₂(IA)₄]. The three complexes show strong fluorescence emissions, and chemosensor behaviors for metal cations are investigated in mixed DMF/H₂O (1?:?9 v/v) solvent. The results reveal that 2 shows effective sensing to Pb²⁺. The mechanism of the detection to Pb²⁺ can be attributed to cation-exchange reaction between cadmium and lead ions.     

Hydrothermal syntheses,crystal structures and thermal stability of two divalent metal phosphonates with a layered and a 3D structure

Two new divalent metal phosphonates, [Cu₂{CH₃C(OH)(PO₃)₂}(H₂O)₂]?·?0.5H₂O (1) and [NH₃CH₂CH₂NH₃][Zn₃{CH₃C(OH)(PO₃)₂}₂(H₂O)]?·?H₂O (2), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. The structure of 1 comprises [Cu₃(hedp)₂]^2? layers connected by [CuO₄] units to form a 3D open-framework structure with a one-dimensional channel system along the b axis. In 2, the connections of alternately arranged [ZnO₄] tetrahedra, [ZnO₆] octahedra and [CPO₃] tetrahedra via vertex-sharing result in a 2D layered structure. The protonated ethylenediamine cations and water molecules are located between adjacent layers.