An unprecedented double-bridging interpenetrating α-Po network based on a new heterometallic cluster {Cu4Mo6}

A new coordination polymer of polyoxomolybdate, {[Cu(4)(bbp)(5)Mo(6)O(22)]·(H(2)O)(4)}(∞) (bbp = 1,4-bis(benzoimidazol-1-yl)phenyl), has been synthesized under solvothermal reaction, which represents a double-bridging interpenetrating α-Po network based on the bimetallic cluster {Cu(4)Mo(6)}. The thermogravimetric and electrochemical behaviors have also been studied.     

Rearrangement of the {Mo6S8}cluster fragment to {Mo4S4} and a New {Mo6S6} Cluster Nucleus: Crystal Structure of K6[Mo4S4(CN)12]·10H2O and (18-Crown-6K)8[Mo6S6(CN)16]·17.5H2O

Two new compounds containing molybdenum thiocyanide cluster anions, K₆[Mo₄S₄(CN)₁₂]·10H₂O (1) and (18-crown-6K)₈[Mo₆S₆(CN)₁₆]·17.5H₂O (2), were synthesized and investigated by X-ray structure analysis. Crystal data: a=11.8430(17), b=11.8430(17), c=35.170(7) , V=4932.8(14) ³, space group I4₁/a, Z=4, d_calc=1.563 g/cm³ for 1; a=28.7513(5), b=18.4190(3), c=20.7586(4) , =118.5982(7)°, V=9651.9(3) ³, space group C2/m, Z=4, d_calc =1.563 g/cm³ for 2. The [Mo₄S₄(CN)₁₂]^6- cluster anion in 1 has an ordinary structure typical of cubane transition metal complexes. In the structure of the [Mo₆S₆(CN)₁₆]^8- anion of 2, two crystallographically independent molybdenum atoms form a Mo₆ metallocluster, represented as two edge-sharing tetrahedra.     

Hydrothermal Synthesis and Crystal Structure of a New Phosphonate： {[Cu（1,10-phen）]2-（H2O3PCH2C6H4C6H4CH2PO3H）2-（HO3PCH2C6H4C6H4CH2PO3H） }n

1 INTRODUCTION Metal organophosphonates have attracted considerable attention for over three decades due to their potential or practical applications, include- ing ion exchanges[1, 2], molecular sensors[3] and optics[4, 5]. Recently, a number of porous m…     

Hydrothermal Synthesis and Structure of a Novel Molybdenum Phosphate: Na4(H3O) [Na(HPO4)2(PO4)4Mo18O49]·16H2O①

The title compound Na5H37P6Mo18O90 1 (Mr=1658) was synthesized under hydrothermal condition and its crystal structure was determined by X-ray diffraction. It crystallized in the monoclinic system, space group P21 with a =14.957(1), b =16.535(1), c = 16.159(1)?,β=108.586(2)°, V=3787.85?3, Dc =3.040g/cm3, Z=2,μ(MoKα)=3.17mm－1, F(000)=3242. The final R and wR are 0.0500 and 0.1535 for 6643 observable reflections with I≥2σ(I), respectively. The result of structure analysis indicates that [Na(HPO4)2(PO4)4－Mo18 O49]5－anions 2 in 1 has the symmetry of C2V, in which each MoVIO6 octahedron is connected to adjacent PO4 tetrahedra through corner-sharing and to adjacent octahedra through edge-sharing or corner-sharing.     

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.     

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.     

Hydrothermal Synthesis and Crystal Structure of a Novel Polymolybdic（VI） Acid： {[H3O]2^＋[Mo2O4（OH）6^]2-}n

1 INTRODUCTION Coordination polymers[1～3] with one-, two- or three-dimensional structure and supramolecular compounds[4, 5] formed by weak interactions, such as hydrogen bonds, Van Der Waals’ forces, short-range exclusion forces, etc., have a variety of possible applications ranging from semicon- ductor to catalysts and potentially valuable pro- perties reminiscent of zeolites. So, considerable increasing attention has been focused on the syn- thesis or building of these coordination po…     

Crystallographic identification of an unusual homoleptic palladium citrate [Na(OH2)6]·{[Na3(OH2)8]3[NaPd3(C6H4O7)3]2}·(H2O) stabilised by intermetallic aggregation with sodium and heavy hydration

A rare precious metal binary citrate represented by palladium in the form of a water-rich Na–Pd intermetallic aggregate has been isolated and crystallographically characterised. It shows a penta-anionic [NaPd3(citrate)3]5? core balanced by [Na3]3+ and Na+ hydrates in a 3-D coordination network stabilised exclusively by citrate bridges and fortified by extensive H-bonding.     

Hydrothermal syntheses and crystal structures of two organic–inorganic hybrid molybdovanadates based on [V2Mo6(OH)2O24]4− and [VMo12O40]3− polyoxoanions

Two new organic–inorganic hybrid cobalt-molybdovanadates [Co(phen)₃]H₂[H₂V₂Mo₆O₂₆] · 7H₂O (1) and [Co(2,2′-bipy)₃][Na(H₂O)₇][VMo₁₂O₄₀] (2) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR, UV, XPS spectroscopy, thermogravimetric (TG) analyses, and X-ray single crystal diffraction. The molecular structure of 1 consists of a [V₂Mo₆(OH)₂O₂₄]^4? polyoxoanion, a [Co(phen)₃]²⁺, two H⁺ and seven lattice water molecules. The structure of [V₂Mo₆(OH)₂O₂₄]^4? consists of six MoO₆ octahedra and two VO₄ tetrahedra; six MoO₆ octahedra are linked by edge-sharing oxygens forming a {Mo₆} ring, and two VO₄ tetrahedra cap opposite sides of the {Mo₆} ring. The molecular structural unit of 2 is constructed from a typical Keggin-type [VMo₁₂O₄₀]^3? polyoxoanion and a [Co(2,2′-bipy)₃]²⁺ cation and a Na⁺ countercation; Co²⁺ is coordinated by six nitrogens from three 2,2′-bipyridines forming a distorted octahedron.     

Syntheses and structures of chalcogen–molybdenum clusters; [Mo3XSe6{S2P(OEt)2}3]Cl, [Mo3X(SeS)3{S2P(OEt)2}3]I and [Mo3 XSe3{S2P(OEt)2}4(py)] (X=0.65S+0.35Se,py= C5H5N)

The trinuclear Mo cluster [Mo3(3–X)(2–Se2)3{S2P-(OEt)2}3]Cl (X=0.65S+0.35Se) (1) has been synthesised by reacting MoCl3·3H2O with ZnSe and [Me4N][S2P(OEt)2] in an EtOH/HCl medium. Reduction of (1) by Ph3P in the presence of [Me4N]-[S2P(OEt)2] and pyridine gave [Mo3(3–X)(2–Se)3 {S2P(OEt)2}4(py)] (X=0.65S+0.35Se, py=C5H5N) (2). Complex (2) was, in turn, converted into [Mo3(3–X)(2–SeS)3{S2P(OEt)2}3]I (X=0.65S+0.35Se) (3) by treatment with H2S and I2. The structures of complexes (1), (2) and (3) were established by X-ray crystallography.     

A three-dimensional porous metal-organic framework based on 9,9-dimethylfluorene-2,7-dicarboxylic acid (H2MFDA): {[Tb2(MFDA)3(DMF)2(H2O)3] · (H2O)3(DMF)6} n

The title metal-organic framework, [Tb₂(MFDA)₃(DMF)₂(H₂O)₃] · (H₂O)₃(DMF)₆} _n (I) (H₂MFDA = 9,9-dimethylfluorene-2,7-dicarboxylic acid, DMF = N,N-dimethylformamide), has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction (CIF file CCDC no. 995892). Complex I crystallizes in triclinic space group \(P\bar 1\) with a = 13.0022(3), b = 13.3793(3), c = 25.8929(4) Å, α = 84.060(2)°, β = 88.104(2)°, γ = 66.361(2)°, V = 4104.05(15) ų, C₇₅H₁₀₄N₈O₂₆Tb₂, M = 1851.50, ρ _c = 1.498 g/cm³, μ(MoK _α) = 1.790 mm^?1, F(000) = 1896, GOF = 1.055, Z = 2, the final R ₁ = 0.0522 and wR ₂ = 0.1380 for I > 2σ(I). In MOF I, the Tb₂ dinuclear units double-bridged by two carboxylate groups are connected together by MFDA ligands to give rise to a 3D architecture that consists in two types of 1D open channels along the y axis with about 6 × 8 and 9 × 12 Ų dimensions. The solvent accessible space for the desolvated I is 53.4% of the total volume. The 3D structure can also be rationalized as a six-connected (3.4¹¹.5².6) topological network by considering the Tb₂ dinuclear units as six-connected nodes and MFDA ligands as linkers, respectively.     

Kristallstruktur von Na3(NH4)12[Mo57Fe6(NO)6O174(OH)3(H2O)24]·76H2O,einer Verbindung mit einem ungewöhnlichen Clusteranion

Summary The X-ray crystal structure of the compound Na₃(NH₄)₁₂[Mo₅₇Fe₆(NO)₆O₁₇₄(OH)₃(H₂O)₂₄]·76H₂O (3) [P6₃/mmc;a=2380.6(5),c=2763.4(7),Z=2], the giant cluster anion of which has the shape of a doughnut, shows remarkable details: The cluster [{Fe(H₂O)₂}₆{Mo(-H₂O)₂(-OH)Mo}₃{ Mo₁₅(MoNO) ₂ ³⁺ O₅₈(H₂O)₂}₃]^15– can be described as being composed of three transferable {Mo₁₇} ligands bridged by cationic centers and contains a novel nanodimensional central cavity.

     

Hydrothermal Synthesis, Crystal Structure and Fluorescent Property of a Novel Mo(Ⅴ) Phosphate [Zn(Mov6P4O31H10)2(C4H14N3)2]·2C4H13N3·8H2O

A new molybdenum phosphate [Zn(Mov6P4O31H10)2(C4H14N3)2]·2C4H13N3·8H2O 1 (C4H13N3 = diethylenetriamine) has been synthesized under hydrothermal condition. Single-crystal X-ray diffraction reveals that compound 1 crystallizes in the monoclinic, space group P21/n, a =13.1679(3), b = 22.1240(6), c = 13.6146(3) (A), β = 103.4847(7)°, V = 3856.95(16) (A)3,C16H90N12O70P8ZnMo12, Mr = 3035.41, Z = 2, Dc = 2.614 g/cm3, μ = 2.483 mm-1, F(000) = 2968, S = 1.014, the final R = 0.0196 and wR = 0.0506 for 7486 observed reflections (I ＞ 2σ(Ⅰ)). Compound 1 consists of two identical rings of six edge-sharing MoO6 octahedra interconnected by one ZnO6 octahedron, whereas the PO4 tetrahedra which share their apices with the MoO6 octahedra are only located on one side of each Mo6 ring. The 2-charge of polyanion [Zn(Mov6P4O31H10)2]2- unit is compensated in the crystal by two mono-protonated diethylenetriamines (C4H14N3)+. By hydrogen bonding interactions the polyanion of compound 1 is interconnected to form pseudo three dimensional molybdophosphate. Other characterizations by elemental analyses, IR spectrum and fluorescent spectrum are also described.     

Synthesis and characterisation of hexanuclear ruthenium clusters containing a μ4-nitrene ligand. Crystal structures of [Ru6(CO)15(μ-CO)2(μ4NH)(μ-OMe)μ3-η2-N(H)C(O)OMe] and [Ru6(CO)16(μ-CO)2(μ4-NH)(μ-OMe)(μ-NCO)]

Two hexaruthenium carbonyl clusters [Ru₆(CO)₁₅(μ-CO)₂(μ₄-NH) (μ-OMe){μ₃-η²-N(H)C(O)OMe}] and [Ru₆(CO)₁₆(μ-CO)₂-(μ₄-NH)(μ-OMe)(μ-NCO)]2 have been isolated from the pyrolysis of H₂Ru₃(CO))₉NOCH₃, and single-crystal X-ray structure analysis shows that both 1 and 2 have a square planar arrangement of four ruthenium atoms capped by a μ₄-nitrene ligand, with two additional ruthenium atoms bridging two opposite RuRu edges of the square base to form a ‘boat’ form metal framework.