吡啶配位的夹心型杂多阴离子{[Na(H2O)2]3[Ni(C5H5N)]3(AsW9O33)2}9-的结构及磁学性质

The pyridine coordinated sandwich-type heteropolytungstate Na7[Ni（H2O）6] { [Na（H2O）2]3[Ni（C5H5N）]3（AsW9O33）2}·28H2O was obtained by the reaction of Na2WO4·2H2O, NaAsO2 and pyridine with NiCl2·6H2O at pH =7.0 and characterized by elemental analysis, IR, UV-Vis,^1H NMR spectra and magnetic measurement. The structure of this heteropolytungstate was determined by X-ray diffraction analysis, which crystallized in triclinic system, space group P1 with a= 1.3153（9） nm, b= 1.7228（12） nm, c=2.6866（19） nm, a=74.130（11）°,β=78.032（12）°, γ = 73.179（12）° and Z= 2, R1 = 0.0604, wR2 = 0.0915 [I〉 2σ（I）]. Polyanion {[Na（H2O）2]3[Ni（C5H5N）]3（AsW9O33）2}^9- has approximately C3 symmetry, and three pyridine coordinated Ni（C5H5N）^2＋ and three Na（H2O）2^＋ are encapsulated between two AsW9O33^9- . Magnetic measurements show that central Ni3 unit in the polyanion exhibits ferromagnetic Ni-Ni exchange interactions （J=6.17 cm^-1）.     

Das Lanthan‐Dodekahydro‐closo‐Dodekaborat‐Hydrat [La(H2O)9]2[B12H12]3·15 H2O und sein Oxonium‐Chlorid‐Derivat [La(H2O)9](H3O)Cl2[B12H12]·H2O

The Lanthanum Dodecahydro‐closo‐Dodecaborate Hydrate [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O and its Oxonium‐Chloride Derivative [La(H₂O)₉](H₃O)Cl₂[B₁₂H₁₂]·H₂O By neutralization of an aqueous solution of the free acid (H₃O)₂[B₁₂H₁₂] with basic La₂O₃ and after isothermic evaporation colourless, face‐rich single crystals of a water‐rich lanthanum(III) dodecahydro‐closo‐dodecaborate hydrate [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O are isolated. The compound crystallizes in the trigonal system with the centrosymmetric space group (a = 1189.95(2), c = 7313.27(9) pm, c/a = 6.146; Z = 6; measuring temperature: 100 K). The crystal structure of [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O can be characterized by two of each other independent, one into another posed motives of lattice components. The [B₁₂H₁₂]²⁻ anions (d(B–B) = 177–179 pm; d(B–H) = 105–116 pm) are arranged according to the samarium structure, while the La³⁺ cations are arranged according to the copper structure. The lanthanum cations are coordinated in first sphere by nine oxygen atoms from water molecules in form of a threecapped trigonal prism (d(La–O) = 251–262 pm). A coordinative influence of the [B₁₂H₁₂]²⁻ anions on La³⁺ has not been determined. Since “zeolitic” water of hydratation is also present, obviously the classical H–O^δ–···^+δH–O‐hydrogen bonds play a significant role in the stabilization of the crystal structure. During the conversion of an aqueous solution of (H₃O)₂[B₁₂H₁₂] with lanthanum trichloride an anion‐mixed salt with the composition [La(H₂O)₉](H₃O)Cl₂[B₁₂H₁₂]·H₂O is obtained. The compound crystallizes in the hexagonal system with the non‐centrosymmetric space group (a = 808.84(3), c = 2064.51(8) pm, c/a = 2.552; Z = 2; measuring temperature: 293 K). The crystal structure can be characterized as a layer‐like structure, in which [B₁₂H₁₂]²⁻ anions and H₃O⁺ cations alternate with layers of [La(H₂O)₉]³⁺ cations (d(La–O) = 252–260 pm) and Cl⁻ anions along [001]. The [B₁₂H₁₂]²⁻ (d(B–B) = 176–179 pm; d(B–H) = 104–113 pm) and Cl⁻ anions exhibit no coordinative influence on La³⁺. Hydrogen bonds are formed between the H₃O⁺ cations and [B₁₂H₁₂]²⁻ anions, also between the water molecules of [La(H₂O)₉]³⁺ and Cl⁻ anions, which contribute to the stabilization of the crystal structure.     

The Nitrogen‐Assisted Triphenylphosphine Displacement of 3‐Hydroxypyridine and 3‐Aminopyridine Ligands in Palladium(II) Complexes: Crystal Structures of [Pd(PPh3)Br]2{μ,η2‐C5H3N(OH)}2 and [Pd(PPh3)Br]2{μ,η2‐C5H3N(NH2)}2

Treatment of Pd(PPh₃₎₄ with 2‐bromo‐3‐hydroxypyridine [C₅H₃N(OH)Br] and 3‐amino‐2‐bromopyridine [C₅H₃N(NH₂)Br] in dichloromethane at ambient temperature cause the oxidative addition reaction to produce the palladium complex [Pd(PPh₃₎₂{η¹‐C₅H₃N(OH)}(Br)], 2 and [Pd(PPh₃₎₂{η¹‐C₅H₃N(NH₂)}(Br)], 3 , by substituting two triphenylphosphine ligands, respectively. In dichloromethane solution of complexes 2 and 3 at ambient temperature for 3 days, it undergo displacement of the triphenylphosphine ligand to form the dipalladium complexes [Pd(PPh₃)Br]₂{μ,η²‐C₅H₃N(OH)}₂, 4 and [Pd(PPh₃)Br]₂{μ,η²‐C₅H₃N(NH₂)}₂, 5 , in which the two 3‐hydroxypyridine and 3‐aminopyridine ligands coordinated through carbon to one metal center and bridging the other metal through nitrogen atom, respectively. Complexes 4 and 5 are characterized by X‐ray diffraction analyses.     

Syntheses,Molecular Structure and Thermodynamic Properties of 3‐Nitro‐1,2,4‐triazol‐5‐one Europium Complex [Eu(NTO)3(H2O)5]·5H2O

3‐Nitro‐1,2,4‐triazol‐5‐one (NTO) europium complex of [Eu(NTO)₃(H₂O)₅]·5H₂O was synthesized by mixing the aqueous solution of lithium 3‐nitro‐1,2,4‐triazol‐5‐onate and the dilute nitric acid solution of europium oxide. The title complex was characterized by elemental analysis and IR spectra. The single crystal structure was determined by a four‐circle x‐ray diffractometer. The title complex is monoclinic with space group P2₁/n and unit cell parameters of a = 1.8720(2) nm, b = 0.6548(3) nm, c = 1.9323(3) nm and β = 95.33(1)°. The coordination geometry around the europium ion is a distorted dodecahedron and there are five crystalline water molecules to form the stable structure of the crystal. From measurements of the enthalpy of solution in water at 298.15 K, the standard enthalpy of formation, lattice enthalpy and lattice energy have been determined as ‐(3798.6 ± 3.7), ?4488.4 and ?4452.4 kJ·mol^?;1, respectively.     

Synthesis and the Unique Crystal Structure of [(H2O)⊂(DB18C6)(μ2‐H2O)2/2][(H3O)⊂(DB18C6)(μ2‐H2O)2/2]I3 (DB18C6 = dibenzo‐18‐crown‐6)

In the title compound 1 , the macrocylic ligand DB18C6 arranges to build two types of channels in which either only water or water and H₃O⁺ molecules are stacked to linear polymers. The counter ions, I₃^—, also form chains and fill in the spaces left between the parallel stacks of the crown ethers. Compound 1 should therefore possess interesting conducting properties and might as well serve as model for biological water channels.     

Synthesis of New Furo[3,4‐b]quinolin‐1(3H)‐one Scaffolds Derived from γ‐Lactone‐Fused Quinolin‐4(1H)‐ones

In the context of our aim of discovering new antitumor drugs among synthetic γ‐lactone‐ and γ‐lactam‐fused 1‐methylquinolin‐4(1H)‐ones, we developed a rapid access to 5‐methyl‐1,3‐dioxolo[4,5‐g]furo[3,4‐b]quinoline‐8,9(5H,6H)‐dione ( 9 ) exploiting the γ‐lactone‐fused chloroquinoline 10 previously synthesized in our laboratory (Scheme 1). We also elaborated efficient synthetic methods allowing for a rapid access to two nonclassical bioisosteres of 9 , i.e., a deoxy and a carba analogue. The deoxy analogue 11 was prepared in two steps from the γ‐lactone‐fused quinoline 13 which was also the synthetic precursor of 10 (Scheme 1). The carba analogue 6,9‐dihydro‐5‐methyl‐9‐methylene‐1,3‐dioxolo[4,5‐g]furo[3,4‐b]quinolin‐8(5H)‐one ( 12 ) was easily prepared by HCl elimination from the 9‐(chloromethyl)dioxolofuroquinoline 15 , which was obtained via a three‐component one‐pot reaction from N‐methyl‐3,4‐(methylenedioxy)aniline (=N‐methyl‐1,3‐benzodioxol‐5‐amine; 16 ), commercially available chloroacetaldehyde, and tetronic acid ( 17 ) (Scheme 2).     

A novel zirconium polyoxometalate compound: (NH4)9[Zr2(μ‐OH)(H2O)2(AsOH)2(AsW7O28)(AsW10O36)]·26H2O

The crystal structure of the title compound, nona­ammonium (arsenic decatungstido)(arsenic heptatungstido)­di­aqua‐μ‐hydroxo‐(hydroxy­arsenido)­di­zir­conium hexa­cosa­hydrate, which was ob­tained from the reaction of [NaAs₄W₄₀O₁₄₀]²⁷⁻ with Zr^IV, has been determined. The anionic complex consists of two hydroxyl‐bridged seven‐coordinate capped trigonal‐prismatic zirconium ions, which are bonded to an [AsW₁₀O₃₆]⁹⁻ anion and to an [AsW₇O₂₈]¹¹⁻ anion that has two {AsOH}²⁺ capping units. The asymmetric unit contains half of the complex, with one crystallographically independent Zr atom. Crystallographic m symmetry imposed by the monoclinic C2/m space group gives rise to the asymmetric unit comprising half of the complex with one crystallographically independent Zr atom.     

Syntheses,Structures and Characterizations of Two Vanadium(V) Complexes:[2-MePyH][V^vO2(C14H9N2O3Br)] and [2-EtPyH][V^VO2(C14H9N2O3Br)]

Two new oxovanadium(V) complexes, [2‐MePyH][V^vO₂(L)] (3) and[2‐EtPyH][V^vO₂,(L)] (4) (salicylaldehyde 5‐bromo salicyloylhydrazone is abbreviated as H₂L; 2‐MePyH is protonated 2‐Mepyridine; 2‐EtPyH presents protonated 2‐Et‐pyridine) were obtained from a reaction of VOSO₄ and H₂L in acetonitrile‐methanol with small quantity of 2‐Me‐pyridine or 2‐Et‐pyridine, and characterized by X‐ray diffraction and spectroscopic methods. Crystal data: [2‐MePyH][VO₂(L)] (3), C₂₀H₁₇N₃O₅BrV, M_r = 510.2, monoclinic, P2₁/n, a = 0.7363(1) nm, 6 = 0.9514(1) nm, c = 2.8594(2) nm, β = 95.305(2)°, Z = 4 and V=1.9946(3) nm³, μ(Mo Kα) = 2.539 mm^?1; [2‐EtPyH][VO₂(L)] (4), C₂₁H₁₉N₃ O₃BrV, M_r = 524.2, triclinic, P1 , a = 0.8051(1) nm, b = 0.9413(1) nm, c = 1.4648(2) nm, α=99.1900(10)°, α = 99.4530(10)°, γ = 104.6670(10)°, Z = 2 and V= 1.0355(2) nm³, μ(Mo Kα) = 2.448 mm^?1, X‐Ray analyses revealed that the crystal structures of 3 and 4 have similar packing modes.     

A Gadolinium Complex of the 5‐(1H‐Tetrazol‐5‐yl)isophthalic Acid Ligand: [Gd(C9H3N4O4)(H2O)3·2H2O]n

The reaction of Gd(ClO₄)₃·6H₂O with 5‐(1H‐tetrazol‐5‐yl)isophthalic acid affords a 3D framework gadolinium coordination polymer, [Gd(C₉H₃N₄O₄)(H₂O)₃·2H₂O]_n ( 1 ). Its crystal structure belongs to a triclinic system, space group , with a = 7.909(2) Å; b = 8.448(2) Å; c = 10.994(2) Å; α = 102.65(3)°; β = 124.32(2)°; γ = 96.28(3)°; V = 704.5(2) ų; Z = 2; R₁ = 0.0245 for 3225 reflections with I >2σ(I), wR₂ = 0.0556. Fluorescent analyses show that compound 1 exhibits purple fluorescence in the solid state at room temperature.     

The Nitrogen‐Assisted Triphenylphosphine Displacement of Methylpyridine Ligand in Palladium(II) Complex: Crystal Structures of [Pd(PPh3)2{η1‐C5H3N(CH3)}(Br)] and [Pd(PPh3)Br]2{μ,η2‐C5H3N(CH3)}2

Treatment of Pd(PPh₃)₄ with 2‐bromo‐4‐methylpyridine, C₅H₃N(CH₃)Br, in dichloromethane at ?20 °C causes the oxidative addition reaction to produce the palladium complex [Pd(PPh₃)₂ {η¹‐C₅H₃N(CH₃)}(Br)], 2 , by substituting two triphenylphosphine ligands. In a dichloromethane solution of complex 2 at room temperature for 3 h, it undergoes displacement of the triphenylphosphine ligand to form the dipalladium complex [Pd(PPh₃)Br]₂{μ,η²‐C₅H₃N(CH₃)}₂, 3 , in which the two 4‐methylpyridine ligands coordinated through carbon to one metal center and bridging the other metal through the nitrogen atom. Complexes 2 and 3 are characterized by X‐ray diffraction analyses.     

Structure of tetra[β‐(1,2,4‐triazole‐l‐yl) propiophenone] dichloro nickel(II) solvate hexahydrate complex: [NiCl2(C2H2N3CH2CH2‐COPh)4]·6H2O

The mononuclear complex, [NiCl₂ (trzCH₂CH₂COPh)₄]·6H₂O (trz =1,2,4‐triazole), was synthesized and its structure was determined by single crystal X‐ray determination. It crystallizes in the monoclinic system, space group P2₁/c, with lattice parameters: a = 0.80391(2) nm, b = 1.08215(2) tun, c = 2.90133(2) nm, β = 94.792 (1)° and Z = 2. Each nickel atom is coordinated by four N atoms of triazole from four β‐(1,2,4‐triazole‐1‐yl)propiophenone ligands and two chloride anions in trans arrangement with octahedral coordination geometry. In addition to the coordinating nickel complex, there are six uncoordinated water molecules. The Ni‐Cl distance is 0.24865(8) nm and the Ni‐N distances are in the range of 0.2072(2) to 0.2099(2) nm, respectively. In the solid state, the title compound forms three dimensional network structure through hydrogen bonds. The intermolecular hydrogen bonds connect the [NiCl₂(C₂H₂N₃CH₂CH₂COPh)₄] and H₂O moieties. The deep green crystals were also examined by elemental analysis, FT‐IR and UV spectra, which are in agreement with the structural data.     

Crystallographic report: Chloro[1,3‐bis[2‐[2‐[(4‐methoxybenzyl) amino]ethylamino]]‐2‐propanol]zinc(II) chloride hydrate, [(C23H36N4O3)ZnCl]Cl·H2O

The zinc(II) center in the molecule of [(C₂₃H₃₆N₄O₃)ZnCl]Cl·H₂O is coordinated by four nitrogen atoms of HL (1,3‐bis[2‐[2‐[(4‐methoxybenzyl) amino]ethylamino]]‐2‐propanol) and one chloro anion. The coordination moieties are connected by hydrogen bonds to form a one‐dimensional structure. Copyright © 2005 John Wiley & Sons, Ltd.