Molecular structure of [In2(μ,η1-OR)(μ,η2-OR)(η2-OR)3(η1-OR)] R = C2H4NMe2, a pincer ligand

Functional indium [In(OR)₃]_m alkoxides (R = C₂H₄OMe, C₂H₄NMe₂) have been obtained by alcoholysis of In[N(SiMe₃)₂]₃ and characterised by elemental analysis, FT-IR and NMR spectroscopy. The 2-dimethylaminoethoxide was characterised by X-ray diffraction. It corresponds to the association of two InO₆ octahedra giving the unsymmetrical dimer [In₂(μ,η¹-OR)(μ,η²-OR)(η²-OR)₃(η¹-OR)] (2). 2 was used as a pincer ligand toward Cu(acac)₂.     

A novel 3-D chiral coordination polymer: hydrothermal synthesis and structural characterization of [Co3(μ3-OH)(μ5-btc)(μ6-Hbtc)(H2O)3·6H2O]n

A chiral 3-D open-framework coordination polymer [Co₃(μ₃-OH)(μ₅-btc)(μ₆-Hbtc)(H₂O)₃·6H₂O]_n was successfully obtained from the mixture of Co(CH₃COO)₂·4H₂O, H₃btc (where H₃btc=benzene-1,2,4-tricarboxylic acid), NaOH and H₂O under hydrothermal condition, which contains a novel and unprecedented coordination mode of btc (see Scheme 1

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Scheme 1. Coordination modes of btc in the compounds having been synthesized. I, μ₄-btc (in the literature [9]); II, μ₆-btc and III, μ₅-btc (see this paper).

).     

Hydrothermal synthesis,crystal structure and physical properties of {[Gd(H2O)4(μ2-C6NO2H5)2Gd(H2O)4](μ3-C6NO2H4)2(ZnCl3)2} · 2H2O · 2Cl

A bimetallic 4f–3d tetranuclear complex {[Gd(H₂O)₄(μ₂-C₆NO₂H₅)₂Gd(H₂O)₄](μ₃-C₆NO₂H₄)₂(ZnCl₃)₂} · 2H₂O · 2Cl (1) has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 is characterized by a tetranuclear Gd₂Zn₂ structure with the gadolinium and zinc atoms interconnected by isonicotinic acid ligands. The tetranuclear species of {[Gd(H₂O)₄(μ₂-C₆NO₂H₅)₂Gd(H₂O)₄](μ₃-C₆NO₂H₄)₂(ZnCl₃)₂} link to isolated chlorine ions and water molecules via π?π interactions and hydrogen bonds to yield a 3-D supramolecular framework. Photoluminescent investigation reveals that the title complex displays an emission in ultraviolet region. The solid-state diffuse reflectance spectra of 1 reveal the presence of a sharp optical gap of 3.66 eV.     

Crystal structure and catalytic studies of heterodinuclear complex [CuZn(μ-OAc)(μ-OH)(μ-OH2)(bpy)2](ClO4)2

The heterodinuclear copper–zinc complex [CuZn(μ-OAc)(μ-OH)(μ-OH₂)(bpy)₂](ClO₄)₂ has been synthesized from solid state reaction and its crystal structure was established. The heterobimetallic complex is quite efficient catalyst for hydrogen peroxide mediated oxidation of alcohols into corresponding carbonyl compounds.     

[Y2(H2O)(BDC)3(DMF)]·(DMF)3: A rare 2-D (42.6)(45.6)2(48.62)(49.65.8) net with multi-helical-array and opened windows

In this work, we present a rare earth metal–organic framework, Y₂(H₂O)(BDC)₃(DMF)]·(DMF)₃ (BDC = 1,3-benzenedicarboxylate) 1, with a rare 2D (4².6)(4⁵.6)₂(4⁸.6²)(4⁹.6⁵.8) net, helical tubes with opposite chirality interweaving of triple-helical chains, opened windows and high thermal stability.     

The novel ligand 4′-phenyl-3,2′:6′,3′′-terpyridine (L) and the supramolecular structure of the dinuclear complex [Zn2(μ-L)(acac)4] · H2O (acac = acetylacetonato)

The new terpyridyl ligand 4′-phenyl-3,2′:6′,3′′-terpyridine (L) reacts with Zn(acac)₂ to produce the dizinc complex [Zn₂(μ-L)(acac)₄] · H₂O (1) (acac = acetylacetonato). The analysis of the crystal structure of this zero-dimensional (0D) complex shows the existence of two Zn(acac)₂ centers bridged symmetrically by one μ-L ligand. The key role played by the acac and L ligands and the guest water molecule allows the generation of a series of intermolecular hydrogen bonds of the O–H/O, C–H/O and C–H/π type which give raise to a 3D supramolecular array. The observed C–H/π interactions are so widespread that all the π-rings present in the structure, viz., those belonging to the L ligand as well as the acetylacetonato chelate rings, participate as hydrogen bond acceptors.     

Ru4(μ-CO)(CO)9(η4-μ4-C6H4)(η2-μ1,μ4-PPhCH2CH2PPh2): an unusual pyrolysis product of Ru3(CO)10(dppe) containing a benzyne ligand

The thermal decomposition of Ru₃(CO)₁₀(dppe) in refluxing benzene gives, in contrast to the pyrolysis of the dppm analogue, the tetranuclear cluster Ru₄(μ-CO)(CO)₉(η⁴-μ₄-C₆H₄)(η²-μ₁,μ₄-PCH₂CH₂PPh₂) (1) along with Ru₃(CO)₉(η²-μ₁,μ₂-C₆H₅)(η³-μ₁,μ₂-PPhCH₂CH₂PPh₂) (2). The single-crystal structure analysis of 1 reveals a square-planar tetraruthenium skeleton containing a η⁴-μ₄-benzyne ligand as well as a η²-μ₁,μ₄-phosphinidene–phosphine ligand.     

One novel near-infrared ytterbium metal–organic framework based on an unprecedented [Yb6(μ2-OH)2(μ3-OH)6]10 + cluster

A novel ytterbium metal–organic framework based on an unprecedented [Yb₆(μ₂-OH)₂(μ₃-OH)₆]^10 + cluster has been obtained and characterized, which shows a rare (3,12)-connected {3².4}₂{3⁸.4²².5²⁴.6¹⁰.7²} topological net and strong near-infrared luminescent emission.     

Terbium-oxalate-pyridinedicarboxylate coordination polymers suggesting the reductive coupling of carbon dioxide (CO2) to oxalate (C2O42−):[Tb2 (3,5-PDC)2(H2O)4(C2O4)]·2H2O and [Tb(2,4-PDC)(H2O)(C2O4)0.5] (PDC = pyridinedicarboxylate)

Under hydrothermal conditions, Tb(NO₃)₃·5H₂O reacted with 3,5-pyridinedicarboxylic acid (3,5-PDCH₂) to give a 3-D coordination polymer with the empirical formula of [Tb₂ (3,5-PDC)₂(H₂O)₄(C₂O₄)]·2H₂O (1). Tb(NO₃)₃·5H₂O also reacted with 2,4-pyridinedicarboxylic acid (2,4-PDCH₂) to give another 3-D coordination polymer [Tb₂ (2,4-PDC)₂(H₂O)₂(C₂O₄)] (2). The structures of both polymers have been determined by X-ray diffraction. X-ray structure analyses show that both polymers contain bridging oxalate (C₂O₄²⁻) ligands, which might have been formed by the reductive coupling of CO₂ molecules released from the PDC²⁻ ligands through the C–C bond cleavage.     

Cyclohexadiene-linked clusters: synthesis and molecular structure of [{Os4(CO)8(MeCCMe)(η6-C6H6)}2(μ2-η2:η2-C6H8-1,3)]

The reaction of [Os₄(CO)₉(RCCR)(η⁶-C₆H₆)] (R=Me, Ph) with Me₃NO in the presence of 1,3-cyclohexadiene or 1,4-cyclohexadiene yields the clusters [{Os₄(CO)₈(RCCR)(η⁶-C₆H₆)}₂(μ₂-η²:η²-C₆H₈-1,3)] and [{Os₄(CO)₈(RCCR)(η⁶-C₆H₆)}₂(μ₂-η²:η²-C₆H₈-1,4)], respectively. The molecular structure of [{Os₄(CO)₈(MeCCMe)(η⁶-C₆H₆)}₂(μ₂-η²:η²-C₆H₈-1,3)] has been determined by single crystal X-ray diffraction, and represents the first example of two osmium cluster fragments linked by 1,3-cyclohexadiene through a μ₂-η²:η²-bridge.     

Synthesis,structural characterization and properties of a novel 1D helical chain arsenomolybdate {[Cu(en)2][Cu(en)(H2O)][(Cu(en)2(H2O)] [AsIIIAsVMo9O34)]} · 2H2O

An organic–inorganic hybrid 1D helical chain arsenomolybdate {[Cu(en)₂][Cu(en)(H₂O)][(Cu(en)₂(H₂O)] [As^IIIAs^VMo₉O₃₄)]} · 2H₂O (1) (en = ethylenediamine) has been hydrothermally synthesized and characterized by elemental analyses, IR, UV and CD spectrum, powder X-ray diffraction, TG-DTA and single-crystal X-ray diffraction. The asymmetric unit of 1 consists of a monocapped trivacant Keggin [As^IIIAs^VMo₉O₃₄]^6 − subunit, a pendant [Cu(en)₂(H₂O)]^2 + cation, a pendant [Cu(en)(H₂O)]^2 + cation, one bridging [Cu(en)₂]^2 + cation and two lattice water molecules. It should be noted that 1 illustrates a one-dimensional (1D) helical chain assembled by {[Cu(en)(H₂O)][(Cu(en)₂(H₂O)][As^IIIAs^VMo₉O₃₄)]}^2 − clusters and [Cu(en)₂]^2 + linkers.     

Eu5(μ4-OH)(μ3-OH)4(μ-DBM)4(DBM)6 (DBM=dibenzoylmethide): a novel Eu5 square-pyramid polynuclear complex with a rare μ4-OH bridging mode

The reaction of EuOCl (EuCl₃) with dibenzoylmethane (HDBM) in the presence of N-methylmorpholine yields a novel Eu₅ square-pyramid polynuclear complex with a rare μ₄-OH bridging mode, Eu₅(μ₄-OH)(μ₃-OH)₄(μ-DBM)₄(DBM)₆ (1). The compound was characterized by elemental analysis, IR, fluorescence and Mössbauer spectra as well as by an X-ray single crystal structure determination. Crystallographic data for 1, C₁₅₀H₁₁₅Eu₅O₂₅, monoclinic, P2₁/c, a=22.223(5), b=17.427(1), c=35.708(5) Å, β=100.11(2)°, V=13614(4) ų, Z=4, R₁=0.0979, wR₂=0.1695.     

Sulfur-assisted chloride and triphenylphosphine dissociation of palladium(II) complex [Pd(PPh3)2(η1-SCNMe2)(Cl)]. X-ray structures of [Pd(PPh3)2(η1-SCNMe2)(Cl)], [Pd(PPh3)(Cl)]2(μ,η2-SCNMe2)2, and [Pd(PPh3)2(η2-SCNMe2)][PF6]

Treatment of Pd(PPh₃)₄ with Me₂NC(S)Cl in dichloromethane at −20 °C produces the complex [Pd(PPh₃)₂(η¹-SCNMe₂)(Cl)], 2. Variable temperature ¹H and ³¹P{H} NMR experiments of complex 2 shows the dissociation of either the chloride or the triphenylphosphine ligand to form complex [Pd(PPh₃)₂(η²-SCNMe₂)][Cl], 3 or the dipalladium complex [Pd(PPh₃)Cl]₂(μ,η²-SCNMe₂)₂, 4. The reaction of complex 2 with NaPF₆ affords complex [Pd(PPh₃)₂(η²-SCNMe₂)][PF₆], 5. Complexes 2, 4, and 5 are characterized by X-ray diffraction analyses.     

First two-dimensional framework material constructed from bicapped Keggin structure clusters: [Cu(en)2(H2O)]{[PMoVI8VIV6O42Cu(en)2][Cu0.5(en)]3} · 5.5H2O

The hydrothermal reaction of CuCl₂ · 2H₂O, Na₂MoO₄ · 2H₂O, NH₄VO₃, ethylenediamine (en) and H₃PO₄ yields a novel two-dimensional open-framework material. The extended structure consists of a network of {PMo₈V₆O₄₂ [Cu(en)₂]}⁵⁻ cages, with each cage connected to three other neighboring units via [Cu(en)₂]²⁺ bridging groups.     

Synthesis,structure of a coordination polymer: {Na2[Zn(C2O4)1.5H2PO4] · 2H2O}n

A phosphatooxalate compound {Na₂[Zn(C₂O₄)_1.5H₂PO₄] · 2H₂O}_n 1 was synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction, IR spectroscopy, thermal gravimetric analysis (TGA) and fluorescent spectroscopy. X-ray single-crystal analysis revealed that its structure was a new mixed inorganic–organic ligand supramolecular framework building up through multilayer assembly.     

A new eight-connected net with CsCl-type topology built on unique [Co2(μ3-OH)(μ2-OH2)(CO2)3]2 building blocks

A new metal-organic framework (MOF) [Co₂(μ₃-OH)(μ₂-OH₂)(oba)(Hoba)(pyz)]_n(1), (oba = 4,4’-oxybis(benzoate), pyz = pyrazine) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, infrared spectroscopy, thermal gravimetric analysis, elemental analysis, and magnetic techniques. The framework defines an eight-connected CsCl net with 4²⁴·6⁴ topology symbol. To the best of our knowledge, this is the first eight-connected CsCl-type net built on unique [Co₂(μ₃-OH)(μ₂-OH₂)(CO₂)₃]₂ molecular building blocks (MBBs).     

A novel uranyl complex UO2(tci)(C3H5N2) · H2O: Synthesis,crystal structure and characterization

Reaction of uranium oxynitrate hexahydrate with tris(2-carboxyethyl)isocyanurate (tciH₃) in acidic aqueous solution (pH ～4–5) yields the compound UO₂(tci)(C₃H₅N₂) · H₂O. X-ray diffraction shows that the uranyl ion is in a hexagonal bipyramid structure. Uranium ion in the complex is found to be ligated with three chelating COO^? groups at the equatorial plane, two oxygen atoms linking to uranium atom formed the vertical axis. The complex has the layered topology structure in the space. The thermal analysis verifies the component and the structure of the complex.