2,3-二甲基吡嗪铜配位聚合物的合成与结构

利用2,3-二甲基吡嗪与硝酸铜及氯化铜合成了铜配位聚合物[Cu(Mepz)]2n+(Mepz=2,3-二甲基吡嗪),并通过单晶X射线衍射方法进行了表征.该晶体属于正交晶系,空间群为:Cmca,相关晶胞参数为:a=0.68617(11)nm,b=1.365 2(2)nm,c=1.953 3(3)nm,V=1.8297(5)nm3.该配位聚合物中的Cu原子与2个N原子、2个O原子和2个Cl原子配位,形成了一个稍微畸变的配位八面体,每相邻的2个配体之间通过Cu离子与吡嗪环上的2个N原子配位连接成无限延伸的一维链状结构,并通过分子间的氢键作用进一步将其连接成为二维的超分子网络结构.     

Synthesen und Kristallstrukturanalysen von [SbI3(SbMe3)(THF)]2 und [Li(THF)4]2[Bi2Cl8(THF)2]

Syntheses and Crystal Structure Analyses of [SbI₃(SbMe₃)(THF)]₂ and [Li(THF)₄]₂[Bi₂Cl₈(THF)₂] The reaction of Me₃Sb with SbI₃ in tetrahydrofuran (THF) gives [SbI₃(SbMe₃)(THF)]₂ ( 1 ). [Li(THF)₄]₂[Bi₂Cl₈(THF)₂] ( 2 ) is formed by reaction of LiCl and BiCl₃ in tetrahydrofuran. The structures of ( 1 ) and ( 2 ) have been determined by X-ray diffractometry. Both structures contain centrosymmetric dimers with the geometry of edge sharing octahedra.     

A polyoxometallate-templated coordination polymer: synthesis and crystal structure of [Cu3(4,4'-bipy)5(MeCN)2]PW12O(40).2C6H5CN

The spherical phosphotungstate ion, PW12O40(3-), has been used as a non-coordinating anionic template for the construction of a novel, three-dimensional Cu(I) coordination polymer.     

Synthesis and crystal structure of triaqua[0.25(bromo)1.75(nitrato-O)]copper(II) 18-crown-6 hydrate (solvate)

A complex triaqua[0.25(bromo)1.75(nitrato-O)]copper(II) 18-crown-6 hydrate (solvate), [CuBr_0.25(NO₃)_1.75(H₂O)₃] · 18-crown-6 · 5H₂O, is synthesized, and its crystal structure is studied by X-ray diffraction analysis (space group Cmc2₁, a = 13.705, b = 14.583, c = 13.174 Å, Z = 4; direct method, full-matrix least-squares refinement in the anisotropic approximation to R = 0.069 for 2547 independent reflections; CAD-4 automated diffractometer, λMoK _α radiation). The mixed complex molecule is a randomly disordered mixture of [Cu(NO₃)₂(H₂O)₃] and [CuBr(NO₃)(H₂O)₃] molecules with site occupancies of 0.875 and 0.125, respectively. The mixed complex molecule and 18-crown-6 molecule lie on the m plane. In the main complex molecule [Cu(NO₃)₂(H₂O)₃], the coordination polyhedron of the Cu²⁺ cation is a slightly distorted square pyramid. The 18-crown-6 molecule has the conformation of a crown with the approximate symmetry D _3d .     

A bis-acetonitrile two-coordinate copper(I) complex: synthesis and characterization of highly soluble B(C(6)F(5))(4)(-) salts of [Cu(MeCN)(2)](+) and [Cu(MeCN)(4)](+)

Copper(I)-acetonitrile complexes are exceedingly useful starting materials for the synthesis of copper(I) complexes with polydentate ligands. To extend the utility of such chemistry to solution studies in relatively low-dielectric solvents (i.e., diethyl ether, toluene) and to aid in obtaining products amenable to X-ray diffraction studies, we have recently begun to employ counteranions such as B(C(6)F(5))(4)(-) for bioinorganic studies. Thus, the synthesis of [Cu(MeCN)(4)]B(C(6)F(5))(4) (1) is presented. Its recrystallization from CH(2)Cl(2)/pentane yields the linear, two-coordinate complex [Cu(MeCN)(2)]B(C(6)F(5))(4) (2), whose centrosymmetric X-ray structure shows that its Cu-N distance is significantly shorter than that in other two-coordinate Cu(I) complexes with nitrogen ligands or that in the tetrahedral complex [Cu(MeCN)(4)]ClO(4). Infrared spectroscopy indicates interesting and diagnostically useful differences between the nu(CN) of 1 and 2.     

A dinuclear molybdenum cluster containing i-mnt ligand: synthesis and crystal structure of [Mo_2S_4(i-mnt)_2] (Et_4N)_2

A dinuclear molybdenum(V) cluster compound (Et4N)2[Mo2S4(i-mnt)2] (i-mnt=l,l-dicyanoethylene-2,2-dithiol, (S2C=C(CN)2]2-) has been prepared by the ligand substitution reaction of Mo2S4(iso-pr2dtp)2 (iso-pr2dtp=S2P(OC3H7)2-) with K2(i-mnt) in the presence of Bt4NI. This cluster was characterized by inrrared spectrum, UV-Vis spectrum and single crystal structure analy-sis. The cluster anion [Mo2S4(i-mnt)2]2- possesses C, symmetry with a crystallographic mirror plane through two bridging S atoms. By the S....S supramolecular interactions between two adjacent cluster anions the [Mo2S4(i-mnt)2]2- anions are linked to form infinite chains along the b axis. Crystal data: monoclinic, space group C2/m, a=1.8748(6), b=1.5360(4), c=1.4322(5) nm, ,β=112.02(2)°, V=3.823(4) nm3, Z=4, Dc=1.50 g/cm3. The final R=0.038 and .RW=0.053 for 3015 observed unique reflections.     

STRUCTURE STUDIES OF [Et_4N]_4[Cu_8(i-mnt)_6] (i-mnt=S_2C=C(CN)_2) AND [Me_4N]_4[Cu_5Ag_3(i-mnt)_6]·H_2O

<正> [Me4N]6[Ag6(i-mnt)6].H2O(1),[Et4N]4[Cu8(i-mnt)6](2) and [Me4N]4-[Cu5Ag3(i-mnt)6].H2O(3)(i-mnt=S2C=C(CN)2) were synthesized. The crystal and molecular structure of the complex 1 was reported by us.The structure of the complex 2 was determined from single crystal X-ray diffraction data. [Et4N]4[Cu8(i-mnt)s] 2, Mr=1870.46, monoclinic, P21/n, a=14.724(6), b = 17.228(3), c=15.59(1)A,β= 100.75(7)°,V=3886.3A3;Z = 2,Dc= 1.598 g/cm3. Complex 3 has been characterized by ICP elemental analyses and IR spectrum.     

The synthesis and crystal structure of a cubane-like tungsten copper sulphur cluster, [W4CuS4 2P(OEt)2 3(I)(μ2-PhCO2)(MeCN)]

Summary The title compound [W₃C₃S₄{S₂P(OEt)₂}₃(I)(₂ ^–PhCO₂)(MeCN)] crystallized in triclinic system with space group P1 and cell dimensiona=11.645(6),b=18.565(2),c=11.292(7)Å, =96.15(3)°, =113.65(3)°, =93.77(3)°, V=2207.6ų, Z=2, Mr=1588.09, D_c=2.39 g cm^–3. MoK radiation, =0.71073 Å, =97.3 cm^–1, F(000)=1488, R=0.042 for 5588 observed unique reflections I3(I). There are some distortions in the cubane-like W₃CuS₄ core, with three W-W bonds and three weak W-Cu bonds. Two W atoms are coordinated by PhCO₂ bridge ligand, the other W atom is coordinated to the N atom of MeCN.     

三水合硝酸钪18-冠-6配合物的合成及其晶体结构

报道了[Sc(NO3)3(OH2)3].(18-冠-6)的合成及其晶体结构.Sc(III)离子同三个双齿配体硝酸根与三个水分子氧配位,构成九配位的配合物.配位多面体是稍有扭曲的单帽四方反棱柱.配位水分子的六个氢原子分别与上下两层冠醚环上的氧原子生成氢键,形成多层夹心分子缔合物.     

Novel crystal engineering in the crown ether nickel maleonitriledithiolate complexes,synthesis and crystal structures of [Na(N15C5)2]2[Ni(mnt)2] and [Na(N15C5)]2[Ni(mnt)2]

Reactions of N15C5 (2,3-naphtho-15-crown-5) with nickel maleonitriledithiolate sodium complex, Na₂[Ni(mnt)₂] (mnt?=?maleonitriledithiolate) using different molar ratios (2?:?1 and 4?:?1) afforded two structurally different complexes [Na(N15C5)₂]₂[Ni(mnt)₂] (1) and [Na(N15C5)]₂[Ni(mnt)₂] (2). The sandwich [Na(N15C5)₂]⁺ and mono-capped [Na(N15C5)]⁺ organic cations are observed in the crystals of 1 and 2, respectively, with the same [Ni(mnt)₂]^2? inorganic conteranions. It is these structurally different organic cations that lead to the dissimilar structures. Complex 1 exhibits a one-dimensional (1D) chain-like structure assembled by intercantionic {[Na(N15C5)₂]⁺}_∞ π–π stacking interactions and electrostatic interactions, while 2 displays a novel two-dimensional (2D) corrugated sheet-like structure constructed by Na–N interactions which occur between the [Na(N15C5)]⁺ inorganic cations and [Ni(mnt)₂]^2? inorganic anions.     

A new cyanobridged one-dimensional coordination polymer based on the octahedral rhenium cluster [Re6Se8(CN)6]4−: Synthesis and crystal structure of [{Cu(H2O)0.5(en)2} {Cu(en)2}Re6Se8(CN)6]·3H2O

The rhenium cluster complex [{Cu(H₂O)_0.5(en)₂} {Cu(en)₂} Re₆Se₈(CN)₆]·3H₂O has been obtained by the reaction of an aqueous solution of K₄[Re₆Se₈(CN)₆]·3.5H₂O with an aqueous solution of Cu(en)₂Cl₂ using cross diffusion through a gel. The structure of the compound has been characterized by a single-crystal X-ray diffraction method (a = 10.690(3) Å, b = 15.035(5) Å, c = 25.847(8) Å, V = 4154(2) ų, Z = 4, space group P2₁2₁2₁, R = 0.0651). Cluster anions [Re₆Se₈(CN)₆]^4? in the complex are connected with Cu²⁺ cations by cyano bridges resulting in zigzag chains. Coordination environment of cations is completed by ethylenediamine molecules. Additionally each cluster anion is coordinated by one terminal fragment {Cu(H₂O)_0.5(en)₂}.     

Calorimetric study of correlated disordering in [Hdamel]2[Cu(II)(tdpd)2] x 2 THF crystal

The heat capacity of [Hdamel]2[Cu(II)(tdpd)2] x 2 THF was measured from 6 to 250 K by adiabatic calorimetry. There are four heat anomalies around 150 K associated with disordering in the orientation of the uncoordinated THF molecules and in the conformation of the out-of-plane allyl groups of [Hdamel](+) units. The total entropy of transition was determined to be 19.8 J K(-1) mol(-1), less than the 4R ln 2 (R = gas constant) expected from the crystal structure at room temperature. The smallness of the total entropy change on phase transitions proves the presence of the strong motional correlation between the adjacent allyl groups. The calorimetric conclusion agreed with the crystal structure at 200 K re-examined in this study.     

Synthesis,X-ray crystal structure and electrochemical properties of (dithiolato)(diimine)copper(II) complexes: [Cu(mnt)(phen)] n and [Cu(dmit)(phen)] 2

Copper (II) complexes [Cu(dmit)(phen)]₂ (1) and [Cu(mnt)(phen)] _n (2) (mnt^2??=?maleonitriledithiolate, dmit^2??=?1,3-dithiole-2-thione-4,5-dithiolate, phen?=?1,10-phenanthroline) have been prepared by ligand-exchange between phen and [N(Bu)₄]₂[Cu(dmit)₂] or [N(Bu)₄]₂[Cu(mnt)₂]. Both complexes have been characterized by spectroscopic, electrochemical, and single-crystal X-ray analysis. In complex 1, dimers are extended into a two-dimensional array by weak S5–Cu contacts. In complex 2, monomers are extended into chains in a head-to-tail arrangement by weak Cu–S coordination bonds and π–π stacking interactions.     

一维链状配位聚合物[Cu(en)2]2[Cu(en)2α-AsⅢ8VⅣ14O42(HPO4)]·8H2O的合成与晶体结构

钒氧化合物由于其有趣的阴离子结构和在催化反应、药物化学以及材料科学等领域中的应用而受到人们的关注[1,2].     

One-dimensional infinite chain crown ether complex:Synthesis and crystal structure of[Na(18C6)]2[Cu(mnt)2]·H2O

One-dimensional coordination polymers have attracted considerable interest in recent years because of the prospect of electrical, optical and magnetic properties. Crown ether can form one-dimensional infinite chain structure with transition metal complex. We synthesized the complexes of 18-crown-6 with Na₂[m{S₂C₂(CN)₂}₂](m=Cu, Ni, Pd, Pt; S₂C₂(CN)₂^2- mnt) and now report the structure of complex[Na(18C6)]₂[Cu(mnt)₂]·H₂O.     

[Cu12S6(PnPr3)8] and [Cu20S10(PnBu1Bu2)8]: Two sulfur bridged copper clusters with Cu-s cluster cores of known compositions but new structures

The synthesis and X-ray determination of two sulfur bridged copper clusters with the known compositions of [Cu₁₂S₆(PⁿPr₃)₈] and [Cu₂₀S₁₀(PⁿBu¹Bu₂)₈] but new molecular structures allow a comparison of these isomeric copper sulfide clusters. The Cu-S frameworks of the clusters with twelve copper atoms are highly topologically related and can both be derived flom a hypothetical naked [Cu₁₂,S₆] cluster that results from theoretical investigations. More dificult is the comparison of the two clusters containing 20 metal atoms. The two cluster types can be called either a prolate or an oblate isomer of [Cu₂₀S₁₀(pR₃)₈].     

Rhenium oxohalides: synthesis and crystal structures of ReO3Cl(THF)2, ReOCl4(THF), Re2O3Cl6(THF)2, and Re2O3Cl6(H2O)2

Convenient methods to prepare solvated rhenium oxochlorides are described; these compounds should serve as useful starting materials for rhenium chemistry. Treatment of perrhenic acid, HReO(4), with chlorotrimethylsilane or with thionyl chloride, followed by addition of tetrahydrofuran, forms the new oxochloride complexes ReO(3)Cl(THF)(2) and ReOCl(4)(THF), respectively. Small amounts of two dinuclear oxochlorides, which evidently resulted from adventitious hydrolysis, were also isolated: Re(2)O(3)Cl(6)L(2), where L = THF or H(2)O. All four compounds were characterized by X-ray crystallography. The rhenium(vii) complex ReO(3)Cl(THF)(2) adopts a distorted octahedral geometry in which the three oxo ligands are in a facial arrangement; the rhenium(vi) complex ReOCl(4)(THF) adopts a trans octahedral structure. The two dinuclear rhenium(vi) compounds both have a single, nearly linear, bridging oxo group; on each Re center, the three terminal chlorides adopt a mer arrangement, and the terminal oxo and the coordinated Lewis base are mutually trans. The water ligand in the aqua complex is hydrogen bonded to nearby THF molecules. IR data are given.