Proton‐stabilized three‐dimensional anionic framework in H[Zn6O2(BO3)3]

A three‐dimensional anionic framework built up from [ZnO₄] tetra­hedra and planar [BO₃] groups, stabilized by H atoms, has been found for hydrogen zinc oxide borate, H[Zn₆O₂(BO₃)₃]. Boron and one of the borate O atoms are on 18e (2) positions. Triple units of [ZnO₄] tetra­hedra sharing a common oxygen vertex on a 12c (3) site and strong asymmetrical linear hydrogen bonds with the H atom [on a 12c (3) position] disordered over a twofold axis are specific structural features of this zincoborate. There is evidence that the reported Zn₄O(BO₃)₂ [Harrison, Gier & Stuky (1993). Angew. Chem. Int. Ed. Engl. 32 , 724–726] corresponds to this structure.     

A three‐dimensional open‐framework zinc arsenate, (C4H12N2)2[Zn7(AsO4)6­(H2O)2]

The title compound, dipiperazinium heptazinc hexakis(arsen­ate) dihydrate, is built from vertex‐sharing AsO₄ tetrahedra, ZnO₄ tetrahedra and ZnO₅ trigonal bipyramids. The connectivity between these polyhedra give rise to an open framework with eight‐ring channels along the crystallographic [001] and [011] directions. The piperazinium cations are located within these channels.     

Synthesis and Crystal Structure of [Cu2（DMF）（H2O）（C7H4NO4）2（C7H3NO4）]2·3.5DMF

A new copper（H） complex [Cu2（DMF）（H2O）（C7H4NO4）2（C7H3NO4）]2-3.5DMF has been synthesized and its structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1^- with a = 10.722（3）, b = 18.170（4）, c = 20.923（7）A,α = 105.297（9）, β = 101.701（10）, γ = 105.74（1）°, V= 3615（1）A^3, Z = 2, C58.50H64.50Cu4N1l.50O3150, Mr = 1686.90, Dc = 1.550 g/cm^3,μ= 1.255 mm^-1, F（000） = 1728.00, T = 150（2） K, the final R = 0.0640 and wR = 0.173 for 11310 observed reflections with I 〉 2σ（I）. In the crystal, each formular unit consists of two dinuclear copper（H） compounds, between which the O-H…O hydrogen bonds exist. Each Cu^Ⅱ cation is six-coordinated in an octahedral geometry. The intermolecular hydrogenbonding interaction leads to a 3-D framework of the title compound.     

三维无机-有机杂化骨架微孔材料──[Co3(BTC)(HBTC)(H2BTC)(C2H4O2)3]·3(DMF)·6(H3O)的合成与结构

沸石和分子筛微孔晶体材料是指以硅酸盐、硅铝酸盐、磷铝酸盐和无机金属磷酸盐为骨架的晶体材料[1,2 ] .最近 ,Yaghi,Williams,Zaworotko,Kitagawa和游效曾等 [3～ 11] 利用刚性和热稳定性较好的有机分子 (如芳香多酸和多碱 )和金属离子作为结构单元 ,制备出了新型无机 -有机杂     

Crystallographic report: A two‐dimensional zinc phosphate framework: [H3N(CH2)3NH3]0.5[Zn2(PO4)(HPO4)]

The two‐dimensional zinc phosphate [H₃N(CH₂)₃NH₃]_0.5[Zn₂(PO₄)(HPO₄)], has been synthesized hydrothermally using 1,3‐diaminopropane as the template. Its structure contains an inorganic framework with three‐, four‐, or six‐membered rings, built from PO₄, PO₃(OH) and ZnO₄ tetrahedral moieties sharing vertexes. The protonated 1,3‐diaminopropane molecules interact with the framework through hydrogen bonds. Copyright © 2004 John Wiley & Sons, Ltd.     

[(C6H10)(NH3)2][Ni(H2O)4C6H2(COO)4]·4H2O – A Coordination Polymer with the Chain‐like Polyanion {Ni(H2O)4[C6H2(COO)4]2−}n

Triclinic single crystals of [(C₆H₁₀)(NH₃)₂][Ni(H₂O)₄C₆H₂(COO)₄]·4H₂O have been prepared in aqueous solution at 55 °C. Space group (Nr. 2), a = 691.23(6), b = 924.84(5), c = 1082.43(7) pm, α = 74.208(6)°, β = 75.558(7)°, γ = 68.251(6)°, V = 0.60985(7) nm³, Z = 1. The Nickel(II) species, located on a crystallographic inversion centre, is coordinated in a trans‐octahedral fashion by two oxygen atoms stemming from the centrosymmetric pyromellitate anions and four from water molecules (Ni–O 205.82(12) – 208.11(13) pm). The connection between Ni²⁺ and [C₆H₂(COO)₄)]^4? leads to infinite chain‐like polyanions extending parallel to with {Ni(H₂O)₄[C₆H₂(COO)₄]^2?}_n composition. [(C₆H₁₀)(NH₃)₂]²⁺‐cations are accomodated between the chains, compensating for the negative charge of the polyanions. Thermogravimetric analysis in air showed that the loss of water of crystallisation occurs in two steps between 102 and 206 °C, corresponding to the loss of 6 and 2 water molecules per formula unit, respectively. The dehydrated sample was stable between 206 and 353 °C. Further decomposition yielded nickel(II) oxide (NiO).     

Selten‐Erd‐Metall‐Koordinationspolymere: Synthesen und Kristallstrukturen von drei neuen Glutaraten, [Pr2(Glu)3(H2O)4] · 10,5H2O, [Pr(Glu)(H2O)2]Cl und [Er(Glu)(GluH)(H2O)2]

Rare‐Earth‐Metal Coordination Polymers: Syntheses and Crystal Structures of Three New Glutarates, [Pr₂(Glu)₃(H₂O)₄] · 10.5H₂O, [Pr(Glu)(H₂O)₂]Cl, and [Er(Glu)(GluH)(H₂O)₂] The new rare‐earth dicarboxylates [Pr₂(Glu)₃(H₂O)₄] · 10.5H₂O ( 1 ), [Pr(Glu)(H₂O)₂]Cl ( 2 ) and [Er(Glu)(GluH)(H₂O)₂] ( 3 ) were obtained from the reactions of glutaric acid with PrCl₃·6H₂O and Er(OH)₃, respectively. The crystal structures were determined by single‐crystal X‐ray diffraction. [Pr₂(Glu)₃(H₂O)₄] · 10,5H₂O crystallizes in the orthorhombic space group Pnma (no. 62) with a = 871.7(4), b = 3105.0(9), c = 1308.3(9) pm and Z = 4. The crystals of [Pr(Glu)(H₂O)₂]Cl are monoclinic (I2/a; no. 15) with a = 786.2(1), b = 1527.6(2) c = 801.2(1) pm, β = 99.78(1)° and Z = 4. [Er(Glu)(GluH)(H₂O)₂] crystallizes in the monoclinic space group P2₁/a (no. 14) with lattice parameters of a = 882.4(1), b = 1375.3(2), c = 1267.4(2) pm, β = 107.13(1)° and Z = 4. The rare‐earth cations have the coordination numbers 10 ( 1 ), 8 + 1 ( 2 ) and 9 ( 3 ). The individual polyhedra are connected to chains and further to sheets in 1 and 2 and to double chains in 3 . Only in the water‐rich compound 1 there are channels that contain crystal water molecules. It, therefore, has a considerably lower density than 2 and 3 .     

一个新颖镍配位阳离子修饰的还原型钼磷酸盐：Ni[Mo6O12(OH)3(PO4)(HPO4)3]2][Ni(H2O)2][Ni(H2O)(bipy)2]4·5H2O

水热合成并通过红外、热重、单晶X-射线衍射表征了一个新颖镍配位阳离子修饰的还原型钼磷酸盐,Ni[Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃]₂][Ni(H₂O)₂][Ni(H₂O)(bipy)₂]₄·5H₂O。单晶X-射线衍射研究表明,两个{Mo₆P₄}簇单元通过一个镍离子连接形成一个Ni[Mo₆P₄]₂二聚结构单元,其进一步和其他的镍配位阳离子连接成钼磷酸盐一维链状结构。在H₂O₂存在下的液－固体系中,使用该化合物催化氧化苯甲醛的探针反应结果表明,该化合物具有较高的催化氧化活性。     

Selten‐Erd‐Metall‐Koordinationspolymere: Synthese und Kristallstrukturen von fünf neuen Adipinaten, [M2(Adi)3(H2O)4](AdiH2)(H2O)4 (M = La,Nd), [Er(Adi)(H2O)5]Cl(H2O) und [M(Adi)(H2O)5](NO3)(H2O) (M = Gd,Er)

Rare‐Earth‐Metal Coordination Polymers: Synthesis and Crystal Structures of Five New Adipinates, [M₂(Adi)₃(H₂O)₄](AdiH₂)(H₂O)₄ (M = La, Nd), [Er(Adi)(H₂O)₅]Cl(H₂O) and [M(Adi)(H₂O)₅](NO₃)(H₂O) (M = Gd, Er) The new rare‐earth compounds [M₂(Adi)₃(H₂O)₄](AdiH₂)(H₂O)₄ (M = La ( 1 ), Nd ( 2 )), [Er(Adi)(H₂O)₅]Cl(H₂O) ( 3 ) and [M(Adi)(H₂O)₅](NO₃)(H₂O) (M = Gd ( 4 ), Er ( 5 )) were obtained from the reaction of adipinic acid with La(OH)₃·xH₂O, Nd₂O₃, ErCl₃·6H₂O, Gd(NO)₃·xH₂O and Er₂O₃, respectively. Their crystal structures were determined by single‐crystal X‐ray diffraction. The coordination polymers [M₂(Adi)₃(H₂O)₄](AdiH₂)(H₂O)₄ crystallize in the triclinic space group (no. 2) with a = 875.4(1), b = 1000.4(2), c = 1179.0(2) pm, α = 74.70(1), β = 69.85(1), γ = 86.18(2)° and Z = 1 (crystal data for M = La, ( 1 )). The quasi‐isostructural compounds [Er(Adi)(H₂O)₅]Cl(H₂O) ( 3 ) and [M(Adi)(H₂O)₅](NO₃)(H₂O) (M = Gd ( 4 ), Er ( 5 )) crystallize with monoclinic symmetry, space group C2/c (no. 15) with lattice parameters of a = 1231.5(1), b = 1532.6(1), c = 895.4(1) pm, β = 123.44(1)° and Z = 4 (crystal data for ( 3 )). The rare‐earth cations have the coordination numbers 10 ( 1 , 2 ) and 9 ( 3 , 4 and 5 ), respectively. The compounds [M₂(Adi)₃(H₂O)₄](AdiH₂)(H₂O)₄ are constructed of infinite chains of edge‐sharig [MO₈(H₂O)₂] polyhedra that are cross‐linked by adipinic acid molecules to form framework structures. In [Er(Adi)(H₂O)₅]Cl(H₂O) ( 3 ) and [M(Adi)(H₂O)₅](NO₃)(H₂O) (M = Gd ( 4 ), Er ( 5 )) the central cations are bridged by adipinic acid molecules in a bidentate‐chelating manner to positively charged zigzag chains. Between these the counter ions and crystal water molecules are incorporated.     

Cerium Complex with Four Types of Ligands: (NH4)6[Ce(H2W12O40)(C4H2O4)(NO3)(H2O)3]

A novel polymer (NH₄)₆[Ce(H₂W₁₂O₄₀)(C₄H₂O₄)(NO₃)(H₂O)₃] ( 1 ) has been constructed at room temperature and characterized by single crystal X‐ray structural analyses, elemental analyses, cyclic voltammetry, IR spectrum, and thermogravimetry. X‐ray structural analysis reveals that through the W–Ot′–Ce–Ob–W linkages a one‐dimension infinitely linear chain with alternating cations and anions is formed. 1 represents the first characterized compound that the Ce³⁺ ions are coordinated by four different types of ligands, and maleinate as ligands in constructing LnPOM architecture.     

Synthesis and Crystal Structure of [La（BTC）（H2O）6]n

1 INTRODUCTION desired topologies owing to their rich coordination modes[8~12] and we have been exploring the chemi- The assembly of metal-organic infinite frame- stry of coordination polymers constructed by tran- works via coordination of metal ions with multifunc- sition metals and benzoic multicarboxylic acids[13~16]. tional organic ligands is a field of increasing inte- In addition, lanthanide ions have high affinity for rest[1~4]. A rational designed and predictable coor- hard donor a…     

Non-Isothermal Decomposion Kinetics of Supermolecule Compound [Eu(C_(10)H_9N_2O_4)(C_(10)H_8N_2O_4)(H_2O)_3]_2·phen·4H_2O

Europium(Ⅲ) compound with 2-oxopropionic acid salicyloyl hydrazone (C_(10)H_(10)N_2O_4,H_3L) and 1,10-phenan-throline (C_(12)H_8N_2,phen) has been prepared.A yellow prismatic crystal of the compound was obtained,and themolecule crystallized in the triclinic space group P-1.There are two 9-coordinated complex molecules in everystructure unit,where every Eu atom is coordinated by three water molecules and two tridentate C_(10)H_(10)N_2O_4 ligands,forming two stable pentacycles.The coordination polyhedron around Eu~(3+) was described as a single cap squareantiprism.In the crystal cell,there are one free 1,10-phenanthroline and four water molecules.The thermaldecomposition of the compound and its kinetics were studied by non-isothermal thermogravimetry.The Kissinger'smethod and Ozawa's method were used to calculate the activation energy value of the first-step decomposition.Thestages of the decompositions were identified by TG-DTG-DSC curve.The non-isothermal kinetic data were ana-lyzed by means of integral and differential methods.The possible reaction mechanism and the kinetic equationswere investigated by comparing the kinetic parameters.     

Die Kristallstrukturen der Polytelluride [Ca(DMF)6]Te4, [Sr(15-Krone-5)2]Te4 · H2O, {[BaCl(18-Krone-6)(DMF)2]2[BaCl(18-Krone-6)(DMF) (H2O)]2(Te4)2} und [Ph3PNPPh3]2Te5 · 2 DMF

Crystal Structures of the Polytellurides [Ca(DMF)₆]Te₄, [Sr(15-Crown-5)₂]Te₄ · H₂O, {[BaCl(18-Crown-6)(DMF)₂]₂[BaCl(18-Crown-6)(DMF) (H₂O)]₂(Te₄)₂}, and [Ph₃PNPPh₃]₂Te₅ · 2 DMF The title compounds were formed by alkalimetal polytelluride solutions in dimethylformamide (DMF) in the presence of the corresponding counter ions as well as in the presence of 15-crown-5 or 18-crown-6. Single crystals were obtained upon using additional diethylether. [Ca(DMF)₆]Te₄: Space group C2/c, Z = 4, 1024 observed unique reflections, R = 0.055. Lattice dimensions at ?70°C: a = 1776.1; b = 813.0 c = 2545.9pm; β = 102.90°. The compound consists of centrosymmetric [Ca(DMF)⁶]²⁺ ions, in which the calcium ions are octahedrally coordinated by the six oxygen atoms of the DMF molecules, and chain-like Te [Sr)15-crown-5)₂]Te₄ · H₂O: Space group C2/c, Z = 4, 3322 observed unique reflections, R = 0.058. Lattice dimensions at ?70°C: a = 1450.5; b = 1407.3; c = 1660.9 pm; β = 110.22°. The compounds forms centrosymmetric cations [Sr(15-crown-5) ₂]²⁺, in which the Sr²⁺ ion is sandwich-like surrounded by the ten oxygen atoms of the crown ether molecules, and chain-like Te₄^2? ions, which are associated in the lattice forming polymeric chains. {[BaCl(18-crown-6)(DMF) ₂]₂[BaCl(18-crown-6)(DMF)· (H₂O)] ₂(Te₄)₂}: Space group P1 , Z = 1, 3189 observed unique reflections, R = 0.054. Lattice dimensions at 19°C: a = 986.1; b = 1052.8; c = 2696.4 pm; α = 89.34°; β = 88.68°; γ = 89.56°. The compound consists of chain-like Te ions without symmetry and of the two somewhat different cations [BaCl(18-crown-6)(DMF) ₂]₂²⁺, in which the Ba²⁺ ions dimerize via centroysmmetric rings. Along with the six oxygen atoms of the crown ether molecules and the oxygen atoms of the DMF molecules, the oxygen atoms of the DMF and water molecule, respectively, the Ba⁺ ions achieve coordination number ten. [Ph₃PNPPh₃]₂Te₅ · 2DMF: Space group Pc, Z = 2, 5971 observed unique reflections, R = 0.058. Lattice dimensions at 20°C: a = 20°C: a = 1085.2; b = 1287.0; c = 2715.9 pm; β = 90.19°. The compounds consists of [Ph₃PNPPh₃]₊ ions, chain-like Te₅^2? ions, and incorporate DME molecules without bonding interaction. The ₅^2? ions are associate via polymeric chains in which left- and right handed individuals are alternating.     

A three‐dimensional inorganic/organic hybrid material, [Ni2(4,4′‐bipy)3(H2O)2V4O12]·2.5H2O

The title compound, poly­[[[di­aqua(μ‐4,4′‐bipyridyl)­di­nickel(II)]‐bis(μ‐4,4′‐bipyridyl)‐di‐μ‐hexa­oxo­di­vana­date(2?)] 2.5‐hydrate], [Ni₂­(V₂O₆)₂­(C₁₀H₈N₂)₃­(H₂O)₂]·­2.5H₂O, has been prepared hydro­thermally and characterized by elemental analyses, IR spectroscopy and single‐crystal X‐ray diffraction. The structure consists of [V₂O₆], [Ni­(4,4′‐bipy)₄O₂] and [Ni­(H₂O)₂­(4,4′‐bipy)₂O₂] polyhedra, and water of crystallization. The Ni atoms and one bipyridyl group lie on centres of symmetry.     

{[Ba2(C2O4)(H2O)6](NCS)2}n: a layered mixed‐anion barium oxalate

We present the first example of a compound containing Ba²⁺, C₂O₄²⁻, water and some additional halide or pseudo‐halide anions, viz. hexa‐μ₂‐aqua‐μ₆‐oxalato‐dibarium(II) diiso­thio­cyanate, {[Ba₂(C₂O₄)(H₂O)₆](NCS)₂}_n. The structure consists of positively charged planar covalent layers of Ba²⁺ cations, oxalate anions and water mol­ecules. The first coordination sphere of the Ba²⁺ cation contains six water mol­ecules and four O atoms from two planar oxalate anions. The oxalate anion lies on an inversion centre and is coordinated to six Ba²⁺ cations, each donor O atom being bonded to two cations. Pairs of water mol­ecules are coordinated by two Ba²⁺ cations. The layers are interspersed with non‐coordinated NCS⁻ anions.     

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.     

A neodymium(III)–ammonium complex involving oxalate and carbonate ligands: (NH4)2[Nd2(C2O4)3(CO3)(H2O)]·H2O

The title compound, di­ammonium aqua‐μ‐carbonato‐tri‐μ‐­oxalato‐dineodymium(III) hydrate, (NH₄)₂[Nd₂(CO₃)(C₂O₄)₃(H₂O)]·H₂O, involving the two ligands oxalate and carbonate, has been prepared hydro­thermally as single crystals. The Nd atoms form a tetranuclear unit across the inversion centre at (,,). Starting from this tetranuclear unit, the oxalate ligands serve to develop a three‐dimensional network. The carbonate group acts as a bis‐chelating ligand to two Nd atoms, and is monodentate to a third Nd atom. The oxalate groups are all bis‐chelating. The two independent Nd atoms are ninefold coordinated and the coordination polyhedron of these atoms is a distorted monocapped antiprism.