Hydrothermal Synthesis of a 1D Paddle-wheel Cu(Ⅱ)Coordination Polymer {[Cu2(NBDOA)2·(H2O)2]·2(H2O)}n Constructed by Flexible Carboxylic Acid

A 1-D paddle-wheel copper (Ⅱ) coordination polymer constructed by 2-nitrobenzene-1,4-di(oxyacetic) acid has been synthesized by hydrothermal reaction, and its crystal structure was determined by X-ray diffraction. The crystal is of triclinic, space group P-1 with a=7.7257(12), b=8.3648(13), c=11.5516(18)(A), α=76.654(2), β=82.088(2), γ=63.636(2)°,C20H22Cu2N2O20, Mr=737.48, V=650.27(18)(A)3, Dc=1.883 g/cm3, F(000)=374, μ=1.737 cm-1 and Z=1. The final refinement gave R=0.0345 and wR=0.0995 for 1996 observed reflections with I ＞ 2σ(Ⅰ). The coordination polymer demonstrates a 1-D microporous structure, and the channel is formed by two NBDOA2- and two Cu2 ions. The ligand NBDOAH2 displays a good flexible characteristic. The 1-D chains are connected to a 3-D supramolecular network by hydrogen bonds.     

Synthesis and Structural Characterization of a Novel 2D Supramolecular Complex {[Dy2Zn(dinic)4(H2O)8]·H2O}n (H2dinic=2,5-Pyridinedicaboxylic Acid)

A new dysprosium-zinc coordination polymer {[Dy2Zn(dinic)4(H2O)8]·H2O}n 1(H2dinic = 2,5-pyridinedicaboxylic acid) has been synthesized and structurally characterized by X-ray analysis. The complex (C28H30Dy2N4O25Zn, Mr = 1212.94) crystallizes in triclinic, space group P-1 with a = 7.8911(16), b = 9.3177(19), c = 13.029(3)(A), α = 75.29(3), β = 75.04(3), γ =79.00(3)°, V = 887.1(3)(A)3, Z = 1, Dc=2.236 g/cm3,μ(MoKα) = 4.947 mm-1, F(000) = 570, the final R = 0.0345 and wR = 0.0903 for 3644 observed reflections with I＞ 2σ(I). A two-dimensional supramolecular structure is formed in 1, which was characterized by elemental analysis, IR, TG analysis, and single-crystal X-ray diffraction.     

Synthesis and crystal structure of a novel tartrate copper(II) two-dimensional coordination polymer: {[Cu2(C4H4O6)2(H2O)2]·4H2O}∞

A new 2D coordination polymer, {[Cu₂(C₄H₄O₆)₂(H₂O)₂]·4H₂O}_∞ has been synthesized by the hydrothermal method and characterized by X-ray single crystal diffraction. Every copper(II) atom adopts a distorted octahedral geometry and coordinates with six oxygen atoms from one water molecule and three tartrate acid ions. The two tartrate acid ions have different coordination modes, one provides four oxygen atoms to coordinate with Cu(II) and another coordinates with all six oxygen atoms. Such a coordination mode generates a two-dimensional coordination polymer. In the solid state, the title compound forms a 3D network structure through hydrogen bonds.     

Hexaaquachromium(III) trihydrogen isopolyvanadate [Cr(H2O)6]H3[V10O28] · 2H2O: Synthesis and study

Hexaaquachromium(III) trihydrogen isopolyvanadate [Cr(H₂O)₆]H₃[V₁₀O₂₈] · 2H₂O (I) was obtained and examined by mass spectrometry, X-ray powder diffraction, thermogravimetry, and IR and NMR spectroscopy. The crystals are monoclinic, space group $P\bar 1$ a = 7.862(3), b = 8.427(5), c = 5.000(2) Å, β = 96.46(4)°, V = 867.0(3) ų, ρ_calcd = 5.83 g/cm³, Z = 1.     

ChemInform Abstract: Unique Seven-Node Rare-Earth Octacyanomolybdate(IV) Three-Dimensional Molecular Frameworks: {[Er(H2O)5(Er (H2O)4)3] [Mo(CN)8]3·11H2O}n and {[Eu(H2O)5(Eu (H2O)4)3] [Mo(CN)8]3·11H2O}n.

Good quality single crystals of the title compound are obtained by reaction of H₄[Mo(CN)₈] with the rare earth carbonates.     

Unique seven-node rare-earth octacyanomolybdate(IV) three-dimensional molecular frameworks: {[Er(H2O)5(Er(H2O)4)3][Mo(CN)8]3·11H2O}n and {[Eu(H2O)5(Eu(H2O)4)3][Mo(CN)8]3·11H2O}n

The crystal structure analyses of {[Er(H₂O)₅(Er(H₂O)₄)₃][Mo(CN)₈]₃·11H₂O}_n (1) and {[Eu(H₂O)₅(Eu(H₂O)₄)₃][Mo(CN)₈]₃·11H₂O}_n (2), show that they are not only new neutral three-dimensional rare-earth octacyanomolybdate(IV) molecular frameworks, but that they also belong to an unknown structure type having seven different nodes. To the best of our knowledge this is different to any other known molybdenum(IV) octacyanide complexes published to date. Both compounds crystallize in the triclinic system, space group P-1, and are isostructural and isotypic. The coordination polyhedra of the molybdenum atoms in the three different [Mo(CN)₈]⁴⁻ anions are trigonal prisms, with two additional atoms. A new bridging mode for octacyanometallates is also observed with five of the eight cyanide groups involved in bridging either three or four rare-earth atoms, while the three remaining cyanide groups are terminal and are involved in hydrogen bonding. The four rare-earth atoms in 1 and 2 have different coordination polyhedra in the form of trigonal prisms with two additional atoms. The three-dimensional structures are made up of infinite two-dimensional slabs linked by one of the rare-earth metal atoms. In both compounds, apart from the 17 coordinated water molecules, there are 11 lattice water molecules of crystallization present in the cavities of the three-dimensional frameworks. The 28 water molecules and the terminal CN⁻ groups are involved in an extensive O–H⋯O and O–H⋯N hydrogen bonding network.     

Synthesis and Structure of One Novel Polyoxometalate Compound Connected via Cerium(Ⅲ) Cation with Three-dimensional Framework H2{[K(H2O)2]2[Ce(H2O)5]2(H2Mo1.16W10.84O42)}·8H2O

One novel polyoxometalate compound connected via trivalent cerium cation as bridge H2{[K(H2O)2]2[Ce(H2O)5]2(H2Mo1.16W10.84O42)}·8H2O 1 was designed and synthesized in aqueous solution. X-ray diffraction analysis reveals that the structure of 1 is a three-dimensional framework assembled from the arrangement of H2Mo1.16W10.84O42 (named paradodecmetalate-B) and Ce(H2O)53 containing two planes, which are constructed through the unification of H2Mo1.16W10.84O4210- and Ce(H2O)53 along the [100] and [001] directions. Crystal data: H96Ce4K4Mo2.32O128W21.68, Mr = 7074.89, monoclinic, P21/n, a = 12.5037(17), b = 17.002(2), c = 12.7473(17) (A), β = 105.966(2)°, V = 2605.4(6) (A)3, Z = 1, Dc = 4.509 g/cm3, F(000) = 3132, μ = 26.098 mm(1, R = 0.0377 and wR = 0.0789 (I ＞ 2σ(I)).     

Synthesis and Structure of One Novel Polyoxometalate Compound Connected via Cerium(Ⅲ) Cation with Three-dimensional Framework H2{[K(H2O)2]2[Ce(H2O)5]2(H2Mo1.16W10.84O42)}·8H2O

One novel polyoxometalate compound connected via trivalent cerium cation as bridge H2{[K(H2O)2]2[Ce(H2O)5]2(H2Mo1.16W10.84O42)}·8H2O 1 was designed and synthesized in aqueous solution. X-ray diffraction analysis reveals that the structure of 1 is a three-dimensional framework assembled from the arrangement of H2Mo1.16W10.84O42 (named paradodecmetalate-B) and Ce(H2O)53 containing two planes, which are constructed through the unification of H2Mo1.16W10.84O4210- and Ce(H2O)53 along the [100] and [001] directions. Crystal data H96Ce4K4Mo2.32O128W21.68, Mr = 7074.89, monoclinic, P21/n, a = 12.5037(17), b = 17.002(2), c = 12.7473(17) (A), β = 105.966(2)°, V = 2605.4(6) (A)3, Z = 1, Dc = 4.509 g/cm3, F(000) = 3132, μ = 26.098 mm(1, R = 0.0377 and wR = 0.0789 (I ＞ 2σ(I)).     

Synthesis and properties of Na6[Pb(S2O3)4] · 6H2O

Conditions for the synthesis of the water-soluble lead thiosulfate complex Na₆[Pb(S₂O₃)₄] · 6H₂O were determined. The complex synthesized was characterized by UV and IR spectroscopy and X-ray phase and thermal analyses. Thermolysis schemes were proposed on the basis of the IR and mass spectra of the thermal decomposition products.     

配位聚合物{[Cu2(nbdo)2·(H2O)2]·2(H2O)}n的热稳定性以及荧光性能和储氢性能

合成了一种新的以柔性羧酸为配体的铜配位聚合物,考察了其热稳定性能、荧光性能及储氢能力.结果表明,配体2-硝基-苯-1,4-二(氧乙酸)表现出较好的柔韧性;该结构在温度低于541 K的环境中比较稳定,当温度高于541 K迅速发生分解并伴随着轻微的爆轰.配合物的荧光光谱与配体的相比有所蓝移.与此同时,该配合物的储氢能力随着氢气压力的增加而提高;当氢气压力为5.0 MPa时储氢能力可达0.42%.     

Two-Dimensional Coordination Polymer {[Zn(Pht)(4.4′-Bipy)(H2O)2] · 2H2O} n : Synthesis and Structure

The coordination polymer {[Zn(Pht)(4,4-Bipy)(H₂O)₂] · 2H₂O} _n (where Pht is a doubly deprotonated phthalic acid residue and 4,4-Bipy is 4,4-bipyridine) was synthesized and studied by X-ray diffraction. It was shown that both ligands perform a bridging function and unite the Zn atoms into a two-dimensional network with a periodicity of 11.302(2) Å (with 4,4-Bipy as the bridge) or 7.627(2) Å (with Pht as the bridge). The coordination polyhedron of Zn is a distorted octahedron with C ₂ symmetry. The Zn–N distances in the coordination polyhedron are 2.117(3) and 2.131(3) Å; the Zn–O_carb distance is 2.171(2) Å and the Zn–O(w) distance is 2.129(2) Å. The O–H···O hydrogen bonds involving the outer-sphere water molecules combine the polymer layers into a framework.     

Synthesis and structure of two molybdovanadates containing coordinatively bound oxalato ligands: (NH4)6[Mo6V2O24(C2O4)2]·6H2O and (NH4)4[H2Mo2V2O12(C2O4)2]·2H2O

The compounds (NH₄)₆[Mo₆V₂O₂₄(C₂O₄)₂]·6H₂O (I) and (NH₄)₄[H₂Mo₂V₂O₁₂(C₂O₄)₂]·2H₂O (II) have been prepared from molybdenum(VI) oxide and ammonium vanadate in aqueous solution through the addition of ammonium oxalate, and their structures determined by X-ray structure analysis. Whereas the molybdovanadate anion [Mo₆V₂O₂₄(C₂O₄)₂]⁶⁻ found in (I) consists of six MoO₆ and two VO₆ edge-sharing octahedra of the γ-[Mo₈O₂₆]⁴⁻ type structure, the tetranuclear anion [H₂Mo₂V₂O₁₂(C₂O₄)₂]⁴⁻ of (II) adopts the structure with a M₄O₁₆ core. Both complexes contain bidentate oxalato ligands bonded to the vanadium ions. In both crystal structures the molybdovanadate anions are mutually hydrogen bonded by ammonium ions and water molecules.     

A polyoxoniobate based on dimeric hexanionbate: [Cu(en)2]4{[Nb6O19H2]K(H2O)5}2 · (H2en) · 17H2O

A polyoxoniobate, [Cu(en)₂]₄{[Nb₆O₁₉H₂]K(H₂O)₅}₂ ? (H₂en) ? 17H₂O (en = ethylenediamine) (1), has been synthesized and characterized by elemental analysis, IR, XPS, TGA, and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P 1, with a = 12.3533(16) Å, b = 12.7188(16) Å, c = 29.626(4) Å, α = 93.235(2)°, β = 96.094(1)°, γ = 106.098(2)°, V = 4429.0(10) ų, Z = 2. The polyoxoanion is composed of a Lindqvist-type [Nb₆O₁₉H₂]^6? dimer bi-bridged via two K⁺. K⁺ is 10-coordinate with 10 oxygens, three from one [Nb₆O₁₉H₂]^6?, one from a terminal oxygen of another [Nb₆O₁₉H₂]^6? moiety, and the other six from water molecule. Adjacent dimeric polyoxoanions are linked to form an infinite 1-D chain via O–H ··· O hydrogen-bonding interactions which exist between the two water trimers and the dimeric polyoxoanions.     

Synthesis, Structure, and Magnetic Properties of One Polyoxometalate (W/Mo) Compound: H8K{[Ni(H2O)5]2(H2Mo1.80W10.20O42)}Cl3·16H2O

One new polyoxometalate compound connected via nickel/potassium cations, H8K{[Ni(H2O)5]2(H2Mo1.80W10.20O42)}Cl3·16H2O 1, was prepared and characterized by elemental analysis and IR spectroscopy. Single-crystal X-ray diffraction analysis results reveal that clusters of [Ni(H2O)5]2(H2Mo1.80W10.20O42)}6-in compound 1 are linked by potassium cations to form one- dimiensional chains, based on which a three-dimensional network is further constructed via the hydrogen bonds of O…O and O…Cl. Magnetic measurements show that compound 1 has para- magnetic properties. Crystal data: H62Cl3KMo1.80Ni2O68W10.20, Mr = 3461.33, monoclinic, space group C2/c, a = 18.9291(19), b = 16.6758(17), c = 19.1064(19)(A), β = 106.6880(10)(, V = 5777.1(10) (A)3, Z = 4, Dc = 3.980 g/cm3, F(000) = 6250, μ = 21.574 mm(1, R = 0.0579 and wR = 0.1623 (Ⅰ ＞ 2σ(I)).     

Synthesis and Structural Characterization of a Polyoxomolybdate HNa7[Mo36O112(H2O)16]·47H2O

A new polyoxomolybdate complex HNa7[Mo36O112(H2O)16]·47H2O 1 has been prepared in the beaker solution and characterized by single-crystal X-ray diffraction and elemental analyses. Crystal data: H127Mo36Na7O175, Mr = 6542.79, monoclinic, C2/c, a = 40.891(6), b =17.900(3), c = 25.580(4) (A), β = 125.673(2)°, V = 15210(4)(A)3, Z = 4, Dc = 2.857 g/cm3, F(000) =12464, μ = 3.013 mm-1, R = 0.0633 and wR = 0.1654 (I＞ 2σ(Ⅰ)). With the bridging sodium cations,the [Mo36O112(H2O)16]8- units in compound 1 are linked to form a one-dimensional structure, on the basis of which a three-dimensional architecture is further constructed via other sodium cations and complicated hydrogen bonds.     

Synthesis and Crystal Structure of Two Decavanadates Cluster Metal Complexes: [Co(H2O)6]2[H2V10O28]·6H2O and (NH4)2[Ca(H2O)7]2[V10O28]

Two new decavanadate metal complexes, [Co(H₂O)₆]₂[H₂V₁₀O₂₈]·6H₂O (1) and (NH₄)₂[Ca(H₂O)₇]₂[V₁₀O₂₈] (2), have been synthesized under hydrothermal condition by using chlorhydric acid as the initiator at 120 °C. The aqueous NaVO₃ solution with an aqueous solution of CoCl₂·6H₂O were used for generating 1 and aqueous CaCl₂·2H₂O and NH₄VO₃ solution were employed for creating 2. Compound 1 consisted of discrete hexa-aqua-cobalt [Co(H₂O)₆]²⁺ cations, [H₂V₁₀O₂₈]⁴⁻ anions and non-coordination water molecules. Compound 2 were composed of hepta-aqua-calcium [Ca(H₂O)₇]²⁺ cations, ammonium NH₄ ⁺ and [V₁₀O₂₈]⁶⁻ anion. For compound 2, the distorted pentagonal bipyramid [Ca(H₂O)₇]²⁺ is uncommon. In the crystal lattice, hydrogen bonds played an important role on connecting cations, anions and non-coordinated water molecules to form the three-dimensional network.     

Cobalt(III) α-Dimethylglyoximates [Co(DH)2(Py)2]2SiF6 · 10H2O and [Co(DH)2(Thio)2]2SiF6 · 2H2O · C2H5OH: Synthesis and Structure

[Co(DH)₂(Py)₂]₂SiF₆ · 10H₂O and [Co(DH)₂(Thio)₂]₂SiF₆ · 2H₂O · C₂H₅OH complexes are synthesized and characterized by X-ray diffraction analysis. Two radicals of -glyoxime linked by hydrogen O–H···O bonds lie in the equatorial plane of the octahedral Co(III) complexes. Intramolecular (– and N–H···O) and intermolecular (O–H···F, O–H···O, N–H···F, N–H···O, N–H···S) interactions are discovered in the crystal. The influence of nonvalence interactions on the structures is discussed.     

Hydrothermal Synthesis of a 1D Paddle-wheel Cu(Ⅱ) Coordination Polymer {[Cu_2(NBDOA)_2·(H_2O)_2]·2(H_2O)}_n Constructed by Flexible Carboxylic Acid

A 1-D paddle-wheel copper (II) coordination polymer constructed by 2-nitro-benzene-1,4-di(oxyacetic) acid has been synthesized by hydrothermal reaction,and its crystal structure was determined by X-ray diffraction. The crystal is of triclinic,space group P1 with a=7.7257(12),b=8.3648(13),c=11.5516(18),α=76.654(2),β=82.088(2),γ=63.636(2)o,C20H22Cu2N2O20,Mr=737.48,V=650.27(18)3,Dc=1.883 g/cm3,F(000)=374,μ=1.737 cm-1 and Z=1. The final refinement gave R=0.0345 and wR=0.0995 for 1996 observed reflections with I > 2σ(I). The coordination polymer demonstrates a 1-D microporous structure,and the channel is formed by two NBDOA2-and two Cu2+ ions. The ligand NBDOAH2 displays a good flexible characteristic. The 1-D chains are connected to a 3-D supramolecular network by hydrogen bonds.     

Synthesis and crystal structure of the nanosized supramolecular SmIII complex with macrocyclic cavitand cucurbituril {[Sm(H2O)4]2(C36H36N24O12)3}Br6·44H2O

The supramolecular compound {[Sm(H₂O)₄]₂(Cuc)₃}Br₆·44H₂O (Cuc = C₃₆H₃₆N₂₄O₁₂) was synthesized. Its crystal and molecular structure was established by X-ray diffraction analysis. The binuclear complex cation {(Cuc)[Sm(H₂O)₄](Cuc)[Sm(H₂O)₄](Cuc)}⁶⁺ built from the alternating cucurbituril molecules (C₃₆H₃₆N₂₄O₁₂) and the [Sm(H₂O)₄]³⁺ aqua ions is a triple-decker nanosized (33 ) sandwich.