Synthesis, characterization, and crystal structures of two new polyoxomolybdate wheel clusters

Two new polyoxomolybdates Na₅(NH₄)₁₆[Mo₅₇Mn₆(NO)₆O₁₇₄ (OH)₃(H₂O)₂₄] · 44H₂O (1) and (NH₄)₂₁[Mo₅₇Cu₆(NO)₆O₁₆₈(OH)₃(H₂O)₂₄] · 53H₂O (2) were synthesized in aqueous solution and characterized by elemental analysis, IR, TG analysis and single-crystal X-ray diffraction. They represent interesting examples of integrating and embedding magnetic 3d metal ions into the diamagnetic polyoxomolybdate host structure.     

Tuning the valence of 3,3-di(1H-tetrazol-5-yl)pentanedioic acid: Solvothermal synthesis of Eu(III) and bimetallic Eu(III)/Cu(II) compounds

3,3-Di(1H-tetrazol-5-yl)pentanedioic acid (H₄dtzpda) with four acidic hydrogen atoms can display different valence when reacted with different metal ions. Solvothermal reactions of H₄dtapda with Eu(NO₃)₃·6H₂O or Eu(NO₃)₃·6H₂O/Cu(NO₃)₂·6H₂O afford [Eu(Hdtzpda)(H₂O)₄]·4H₂O (1) and [Eu₂Cu(dtzpda)₂(H₂O)₁₀]·6H₂O (2), respectively, where only three acidic hydrogen atoms of H₄dtzpda are deprotonated in compound 1 while all the four acidic ones are deprotonated in compound 2. In compound 1, Hdtzpda^3 − acts as a pentadentate ligand to bridge Eu(III) centers via the oxygen atoms of the carboxylate group while in compound 2, dtzpda^4 − is a hepadentate one via not only the oxygen atoms of the carboxylate group but also the nitrogen atoms of the tetrazole rings. The luminescence properties of the two compounds in the solid state show both intraligand and characteristic peaks of Eu^3 + at room temperature.     

The hydrothermal synthesis and structure of a one-dimensional Fe(II)molybdophosphate

A new one-dimensional Fe(II)molybdophosphate of the formula, [(C₁₀H₈N₂)H₂]₂[Fe₄^(II)Mo₁₂^(V)(HPO₄)₆(PO₄)₂(H₂O)₈(OH)₆O₂₄]·8H₂O, (1), has been synthesized by employing hydrothermal methods and characterized by single crystal X-ray diffraction. The structure consists of a network of MO₆ (M = Fe, Mo) octahedra and (H)PO₄ tetrahedra linked through their vertices. The connectivity between the polyhedral units gives rise to one-dimensional chains with eight-membered apertures. The hydrogen bonded interactions between the chains form pseudo two-dimensional layers. Extensive hydrogen bonding also exists between the amine molecule, 4,4^′-bipyridine, water molecule and framework oxygen atoms. Crystal data for 1: monoclinic, space group = P2₁ (no. 4), a=12.549(3) (Å), b=23.496(5) (Å), c=14.551(3) (Å), β=114.87(3)°, , and Z=2.     

Solvothermal synthesis of 1D and 2D cobalt(II) and nickel(II) coordination polymers with 2,5-dihydroxy-p-benzenediacetic acid

1D cobalt(II) and nickel(II) coordination polymers {[Co(dba)(H₂O)₄] · H₂O}_n (1) and {[Ni(dba)(H₂O)₄] · H₂O}_n (2) (H₂dba = 2,5-dihydroxy-p-benzenediacetic acid) were synthesized under low temperature solvothermal condition. When 4,4′-bipyridine (bpy) was introduced to the synthetic systems of 1 and 2, respectively, two novel 2D coordination polymers {[Co(dba)(bpy)] · 0.5H₂O}_n (3) and [Ni(dba)(bpy)(H₂O)₂]_n (4) with different structures were obtained. All of the compounds were characterized by elemental analysis, FT-IR, UV–Vis spectra and single crystal X-ray diffraction.     

Self-assembly through hydrogen-bonding and C–Hπ interactions in metal complexes of N-functionalised glycine

The complex [Ni(L1)₂(py)₂]. toluene (L1 is N-phthaloylglycinato and py is pyridine) was prepared from solid state reaction whereas co-crystals having composition 2[Ni(L1)₂(py)₃(H₂O)] · [Ni(L1)₂(py)₂(H₂O)₂] · 2py · 2H₂O was obtained from solution state reaction.     

Two novel Zn(II) coordination polymers based on trigonal ligand: 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine

Two novel Zn(II) coordination polymers, [Zn₅(pytpy)₈(fum)₄(H₂O)₄(OH)₂]_n · n(CH₃OH) · 2n(H₂O) (1) and [Zn₃(pytpy)₄ (btc)₂]_n · 2n(H₂O) (2) (pytpy = 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine, H₂fum = fumaric acid, H₃btc = 1,3,5-benzenetricarboxylic acid) have been hydrothermally synthesized and structurally characterized. Complex 1 is a 2D layer structure, which is constructed from linear pentanuclear Zn(II) subunits interconnected via bidentate-bridging pytpy ligands and tridentate-bridging fum²⁻ anions. Complex 2 is a 3D network structure, μ₂-pytpy ligands link the layers based on the heart-like hexanuclear subunits to form the 3D network. Both complexes show strong fluorescence emission upon excitation at 310 nm in solid state. Additionally, these two complexes possess great thermal stabilities, especially for 2, the framework is stable up to 350 °C.     

An unprecedented 2D isopolymolybdate with (3·4)(3·5·8)(3·4·5·6·8)(3·4·5·6) topology

A novel two-dimensional molybdenum oxide polymer, [Mo₄O₁₃]_n · 2nH₃O, has been prepared under specific hydrothermal conditions and characterized by IR spectroscopy and TG analysis. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a (3, 4, 5, 6)-connected 2D layer structure with (3²·4)(3²·5³·8)(3·4²·5⁴·6·8²)(3⁴·4³·5⁴·6⁴) topology, which is constructed by two parallel molybdenum oxide dimeric chains (Mo₂O₁₀)_n bound together by the dimer of Mo₂O₉ subunits via the sharing of corners. Additionally, the electrochemistry activity of compound 1 is also reported.     

A new (3,4,7)-connected topology framework based on [Cd2(CO2)3O4N2] second building unit

A new 3D coordination polymer [Cd₂(L³)(BTC)(H₂O)] (1) (HL³ = 3,5-bis(pyridin-3-ylmethoxy)benzoic acid, H₃BTC = 1,3,5-benzenetricarboxylic acid), has been isolated under hydrothermal condition and characterized by single-crystal X-ray diffraction. Compound 1 is constructed from Cd₂-based second building units (SBUs) [Cd₂(CO₂)₃O₄N₂] and displays a 3D (3,4,7)-connected net with (4²·6)(4³·6³)(4⁵·6¹¹·8⁵) topology. In addition, the photoluminescent spectra indicate compound 1 may be a good candidate for blue-luminescent materials.     

An unusual dichromium(II,II) compound bearing di-2-pyridyl ketone oximate ligands and prepared by the ligand-assisted reduction of a trichromium(III,III,III) complex in air

The reaction of the oxide-centred triangular, trichromium(III,III,III) complex [Cr₃O(O₂CCMe₃)₆(H₂O)₃](O₂CCMe₃) with di-2-pyridyl ketone oxime, (py)₂CNOH, in MeCN under aerobic and refluxing conditions yields the pivalate-free, dichromium(II,II) complex [Cr₂{(py)₂CNO}₄] · 2H₂O (1 · 2H₂O). The dinuclear complex can also be prepared by the reaction of [Cr(CO)₆] with (py)₂CNOH in refluxing MeCN/H₂O in air. The two high-spin Cr^II atoms are doubly bridged by two 2.1110 oximate ligands, while a chelating 1.0110 (py)₂CNO⁻ ion completes distorted trigonal bipyramidal coordination at each metal centre. The dimers are stabilized by intramolecular stacking interactions between the terminal (py)₂CNO⁻ ligands, and the structural effects of these interactions are discussed.     

Formation of an unusual copper(II) complex from the degradation of a novel tricopper(II) carbohydrazone complex

An unusual copper(II) complex [Cu(L^1a)₂Cl₂] CH₃OH·H₂O·H₃O⁺Cl⁻ (1a) was isolated from a solution of a novel tricopper(II) complex [Cu₃(HL¹)Cl₂]Cl₃·2H₂O (1) in methanol, where L^1a is 3-(2-pyridyl)triazolo[1,5-a]-pyridine, and characterized with single crystal X-ray diffraction study. The tricopper(II) complex of potential ligand 1,5-bis(di-2-pyridyl ketone) carbohydrazone (H₂L¹) was synthesized and physico-chemically characterized, while the formation of the complex 1a was followed by time-dependant monitoring of the UV–visible spectra, which reveals degradation of ligand backbone as intensity loss of bands corresponding to O → Cu(II) charge transfer.     

An oxide chain constructed from octamolybdate, a Keggin anion and a copper (II) – Tetrapyridylpyrazine binuclear unit

The hydrothermal reaction of MoO₃, CuSO₄·5H₂O, tetra-4-pyridylpyrazine (tpyprz), and diphenyldiarsonic acid in water at 140 °C for 48 h yielded the one-dimensional material [{Cu₂(tpyprz)(H₂O)₃}₂{Mo₈O₂₆}{Mo₁₂O₃₆(AsO₄)}]·8H₂O (1·8H₂O). The chain structure of 1·8H₂O is constructed from alternating β-octamolybdate clusters and molybdoarsonate Keggin clusters linked through {Cu₂(tpyprz)(H₂O)₃}⁴⁺ binuclear subunits. The Cu(II) sites are inequivalent with one copper bonding to two pyridyl donors and a pyrazine nitrogen of one terminus of the tpyprz ligand, two aqua ligands and an oxo-group of the cluster while the second copper site coordinates to the nitrogen donors of the other terminus of the tpyprz ligand, an aqua group, a terminal oxo-group of the cluster and a terminal oxo-group of the mixed valence {Mo₁₁^VIMo^VO₃₆(AsO₄)}⁴⁻ cluster. Crystal data: C₄₈H₆₀AsCu₄Mo₂₀N₁₂O₈₀: FW = 4332.96 Triclinic , a = 12.5087(5) Å, b = 13.6681(6) Å, c = 14.8980(6) Å, α = 92.196(1)°, β = 97.046(1)°, γ = 97.751(1)°, Z = 1, D_calc = 2.877 g cm⁻³; structure solution and refinement based on 12,333 reflections (Mo K_α, λ = 0.71073 Å) converged at R₁ = 0.0540 and wR₂ = 0.1115.     

Unusual formations of superoxo heptaoxomolybdates from peroxo molybdates

Two novel dioxygen heptaoxomolybdates K₅[Mo₇O₂₂(O₂)(OH)]Cl·6H₂O (1) and K₅[Mo₇O₂₂(O₂)(O₂)]·8H₂O (2) were isolated from the solution of peroxo molybdate accidently. The solids were characterized by IR, EPR and X-ray single crystal analysis. Complex 1 contains a superoxo group with a short bond distance 1.27(1) Å, while 2 is a mixed complex with peroxo and superoxo groups [1.43(1), 1.27(1) Å]. All of the dioxygen groups coordinate to molybdenum atoms in side-on (η²) fashion. The two complexes are short-lived and will decompose into peroxo molybdates K₅[Mo₇O₂₁(O₂)₂(OH)]·6H₂O (3) and K₆[Mo₇O₂₂(O₂)₂]·9H₂O (4) very quickly.     

A three-dimensional zincic molybdenum (V) phosphate with helical channel: Synthesis,structure, and electrochemical properties

A new reduced zincic molybdophosphate, (H₂bpp)₃[Zn₃Mo₁₂^VO₂₄(OH)₆(H₂O)₂(HPO₄)₆(PO₄)₂]·2H₂O 1 (bpp = 1,3-bis(4-pyridyl)propane) has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, and single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal space group I 41/a c d with a = 31.8033(4) Å, b = 31.8033(4) Å, c = 34.5593(8) Å, V = 34955.0(10) ų, and Z = 16 and exhibits a 4,6-connected 3-D framework with (3².8⁴)(3⁴.4².8³.9⁵.10) topology. The basic building blocks of [Zn(2)(Mo₆P₄)₂] are linked through [Zn(3)O₆] octahedra and [Zn(1)O₄] tetrahedra to construct 1-D chains along four different directions. Such 1-D chains are further connected by [Zn(1)O₄]²⁺ linkers to form a 3-D intricate framework with helical channels occupied by protonated bpp and water molecules. Additionally, the electrochemical property of the 1-CPE has been studied in detail.     

Syntheses, structures, and photoluminescence of two Cd(II) coordination polymers constructed from analogue (pyridyl)imidazole derivative and polycarboxylate acid

Two novel Cd(II) coordination frameworks based on a semirigid asymmetric ligand L and aromatic multi-carboxylate ligands, {[Cd₂L(btc)(H₂O)₂]·5H₂O}_n (1) and [Cd₂L₂(bdc)]_n (2) (L = (4-((2-(pyridine-2-yl)-1H-imidazol-1-yl)methyl)benzoic acid, H₃btc = 1,3,5-benzenetricarboxylic acid, H₂bdc = 1,3-benzenedicarboxylic acid), have been hydrothermally synthesized, and structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography. Due to various coordination modes and conformations of the semirigid asymmetric ligand, and carboxylate containing co-ligands, therefore, the two complexes exhibit structural and dimensional diversity. Complex 1 exhibits a novel 2D (3, 5)-connected network structure with (3·5²)(3²·5³·6⁴·7) topology. Complex 2 exhibits a novel 3D CdSO₄ topology, which is formed from different dinuclear cadmium units. In addition, the photoluminescence properties of the free ligand L, and complexes 1 and 2 were studied in the solid state at room temperature.     

Photoinduced linkage isomerism of binuclear bis(pyrazole-3,5-dicarboxylato)-bridged {RuNO} centres

The two novel binuclear pyrazole-3,5-dicarboxylato-bridged {RuNO}⁶ complexes K₂[{Ru(NO)Cl}₂(μ-pzdc)₂] (1) and [{Ru(NO)(H₂O)}₂(μ-pzdc)₂]·4H₂O (2) (pzdc = pyrazole-3,5-dicarboxylate) were synthesized and characterized by elemental analysis, mass spectrometry and spectroscopic methods (NMR, UV–vis, IR). 2 was investigated by means of single-crystal X-ray diffraction analysis. On irradiation, in both 1 and 2 the existence of photoinduced long-lived metastable isonitrosyl states SI were detected by low-temperature infrared spectroscopy.     

A weak-link approach to the synthesis of copper(II)-based metallacycles using a flexible hemilabile 4,7-diazadecanediamide ligand

Employment of a weak-link approach to the synthesis of Cu(II) metallacycle [Cu₂(C₈H₁₈N₄O₂)₂(C₂H₈N₂)₂] · 4Cl (2) from [Cu(C₈H₁₈N₄O₂)(Cl)]Cl · 2H₂O (1) under very mild reaction conditions was achieved in high yield using a flexible hemilabile multidentate ligand, 4,7-diazadecanediamide.     

Syntheses,crystal structures and luminescent investigations of cobalt(II) and zinc(II) complexes with 2-propyl-4,5-dicarboxylate-imidazole (H3PIDC)

Presented in this communication are four metal complexes based on 2-propyl-4,5-dicarboxylate-imidazole (H₃PIDC), including two Co(II) coordination compounds, [Co(H₂PIDC)₂(H₂O)₂] · 4H₂O (1) and 2[Co(H₂PIDC)₂(H₂O)₂] · 5H₂O (2), as well as two Zn(II) coordination compounds, [Zn(H₂PIDC)₂(H₂O)₂] · 4H₂O (3) and 2[Zn(H₂PIDC)₂(H₂O)₂] · 7H₂O (4). They contain the same coordinated unit of [M(H₂PIDC)₂(H₂O)₂] (M = Zn or Co). Interestingly, among these four complexes, 1 and 2, or 3 and 4 crystallized in different space group, which may be related with the number of the crystallized H₂O molecules.     

Synthesis and structure of a high-nuclearity oxomolybdenum(V) complex, [Mo12O28(OC2H5)4(C6H7N)8]

(PyH)[MoOBr₄(H₂O)]·2/3PyHBr (PyH⁺=pyridinium cation, C₅H₅NH⁺) yielded upon the solvothermal reaction with ethanol and 4-methylpyridine (4-MePy, C₆H₇N) a novel oxoethoxomolybdenum(V) cluster, [Mo₁₂O₂₈(OC₂H₅)₄(4-MePy)₈] 1. Molybdenum atoms are grouped into six Mo^V₂ pairs linked by single metal–metal bonds. Three crystallographically independent Mo–Mo distances are 2.5578(14), 2.5981(14) and 2.6489(16) Å.     

Synthesis and structural characterization of an alternating double aquo-bridged and single cyano-bridged polymeric barium–iron complex: {[Ba2(phen)4(H2O)6Fe(CN)6]·Cl·2(phen)·3H2O}n

A new alternating double aquo-bridged and single cyano-bridged polymeric complex {[Ba₂(phen)₄(H₂O)₆Fe(CN)₆]·Cl·2(phen)·3H₂O}_n (1) (phen = 1,10-phenanthroline) has been synthesized and structurally characterized. In the crystal structure the two centrosymmetric [Ba₂(phen)₄(H₂O)₆] units are bridged through two trans CN groups of [Fe(CN)₆]³⁻ ion, which results in the formation of a zig-zag polymeric chain. In each [Ba₂(phen)₄(H₂O)₆] unit, the two Ba centers are joined by double aquo bridges. Both the Ba atoms are 9-coordinated with distorted mono-capped square antiprismatic geometry. An elaborate hydrogen bonding system holds the parallel polymeric chains together.     

A new binuclear potassium (І) complex with a novel 1D infinite water chain containing (H2O)12 clusters

A novel 1D infinite water chain made of (H₂O)₁₂ clusters containing two different chair water hexamers is found in the binuclear coordination compound, [K₂(L)₂(phen)₄]·6H₂O (1) (where L = 2,2′-azanediyldibenzoic dianion, phen = 1,10′-phenanthroline), which has been synthesized and structurally characterized by single-crystal X-ray diffraction. The fluorescence spectrum and thermogravimetric analysis (TGA) of the title complex 1 have been also discussed.