配合物[Co(phendione)(SO4)(H2O)]·5H2O的合成及表征

在水和甲醇的混合液中合成了标题配合物[Co(phendione)(SO4)(H2O)]·5H2O (phendione=1,10-菲啰啉-5,6-二酮),通过元素分析,红外光谱和热分析对配合物进行了表征.结果表明,配合物中Co(Ⅱ)与2个N原子和2个O原子形成4配位结构,其中2个N原子来自配体1,10-菲啰啉-5,6 -二酮,2个O原子分别来自1个水分子和1个硫酸根离子.根据热分解曲线,初步探讨了该配合物的热分解机理,热分解最终产物为CoO.     

Synthesis and structure determination of a new layered zincophosphate: [H2N2C6H16]0.5[Zn2(PO4)(HPO4)(H2O)]·H2O

The synthesis and crystal structure of a new microporous zincophosphate are described. [H₂N₂C₆H₁₆]_0.5[Zn₂(PO₄)(HPO₄)(H₂O)]·H₂O crystallizes in the triclinic space group P1¯ with a = 8.822(4), b = 9.236(4), c = 8.451(3) Å, = 67.19(3), = 91.32(3), = 111.10(3)°, V = 586.7(4) ų and Z = 2. This new material consists of infinite two-dimensional anionic layers alternated with planes containing organic diprotonated templates, N, N, N, N-tetramethylethylenediamine [H₂N₂C₆H₁₆]²⁺ molecules. The framework structure is built up of ZnO₄, ZnO₃OH₂, PO₄, and PO₃OH tetrahedra, linked through oxygen vertices. The presence of terminal OH₂ and OH groups, leads to an open structure containing four- and eight-rings. The organic molecules are interconnected to the framework through hydrogen bonds.     

Metal-hydroxycarboxylate interactions: syntheses and structures of K2[VO2(C6H6O7)]2·4H2O and (NH4)2[VO2(C6H6O7)]2·2H2O

Potassium and ammonium dimeric (citrato)dioxovanadium(V) hydrate K₂[VO₂(H₂cit)]₂·4H₂O1 and (NH₄)₂[VO₂(H₂cit)]₂·2H₂O2 (H₄cit=citric acid) have been prepared and characterized by X-ray structure analyses. Vanadate1 crystallizes in the monoclinic space groupP2₁/n (No. 14) with unit cell parameters:a=9.304(2),b=11.756(2),c=11.911(2)Å, =111.72(3)°, andD _c=1.911 g/cm³,Z=2; Vanadate2 also crystallizes in the monoclinic space groupP2₁/n with unit cell parameters:a=9.719(2),b=11.111(3),c=11.294(2)Å, =109.03(2)°, andD _c=1.781 g/cm³,Z=2. Each dimer contains a centro-symmetric planar four-member V₂O₂ ring with two exocyclic citrate entities coordinated by the oxygen atoms of the hydroxy-and -carboxylate ligands, while the other two -carboxylate groups remain uncomplexed. Principal dimensions of the V–O bonds are 1.986(4)_av (hydroxy) and 1.980(3)Å(-carboxyl) for vanadate1, 1.988(2)_av (hydroxy) and 1.974(3)Å(-carboxyl) for vanadate2.     

Synthesis, crystal structure, and thermal analyses of triaqua-(1,10-phenanthroline-N,N′) succinatomanganese(II) dihydrate, [Mn(H2O)3(phen)(C4H4O4)]·2H2O

[Mn(H₂O)₃(phen)(C₄H₄O₄)]·2H₂O was obtained by reaction of freshly prepared MnCO₃, phen and succinic acid in CH₃OH/H₂O (1:1 v/v), and its crystal structure has been determined by single crystal X-ray diffraction methods. The title mixed ligand complex crystallizes in the triclinic space group with cell dimensions a = 7.590(1) Å, b = 9.324(1) Å, c = 13.917(1) Å, = 85.64(1)°, = 74.56(1)°, = 77.10(1)°, and D _calc = 1.584 g/cm³ for Z = 2. The crystal structure consists of the [Mn(H₂O)₃(phen)(C₄H₄O₄)] complex molecules and lattice H₂O molecules. The Mn atoms are each octahedrally coordinated by two N atoms of one phen ligand and four O atoms of three H₂O molecules and one succinato ligand with d(Mn—N) = 2.271 and 2.299 Å, and d(Mn—O) = 2.133–2.239 Å. Through intermolecular hydrogen bondings, the complex molecules are interlinked to form 2D layers, which are assembled by – stacking interactions into 3D framework with tunnels occupied by the lattice H₂O molecules. Thermal analyses showed that the title compound decomposes in two steps over the range 25–600°C upon heating in flowing Ar.     

[Co(dmg)2Cl2]3·[Co(dmg)2Cl(OH)]·[Co(dmg)(phen)]·(H2O)4的合成和晶体结构

本文合成了一个复杂的单核配合物 [Co(H2dmg)2Cl2]3·[Co(H2dmg)2Cl(OH)]·[Co(Hdmg)(phen)]·(H2O)4 (H2dmg＝dimethylglyoxime, phen＝1,10-Phenanthroline).通过X射线衍射技术获得其单晶结构.在单晶结构中,每五个单核钴(II)的配位结构形成一个重复单元,是一个较为复杂的单晶.其空间群为P-1,晶胞参数为a＝1.3738nm;b＝1.4396nm;c＝1.8656nm.本文中我们将讨论该化合物的分子结构及相关光谱性质.     

Structural and spectroscopic characterization of the macrocyclic complex: [Tb(CrO4)(H2O)(C22H26N6)] ·0.5(Cr2O7)·(H2O)

The title complex was obtained by anion metathesis from [Tb(CH₃COO)₂(C₂₂H₂₆N₆)] (CH₃COO)·4H₂O and K₂CrO₄ in aqueous solution. The compound crystallizes in the triclinic space group witha=8.384(2),b=10.425(2)c=15.752(2)Å, =98.82(2), =93.52(2), =97.22(2)°, andZ=2. The structure is ionic and consists of a (+1) complex cation balanced in a 21 ratio by a disordered dichromate ion. The 9-coordinate Tb(III) is linked to the six nitrogen atoms of the macrocyclic ligand L=C₂₂H₂₆N₆, as well as to a water molecule and a bidentate chelating chromate situated on opposite sides of the macrocycle. The infrared spectrum shows, in addition to the pattern of the macrocyclic ligand, the absorptions arising from the stretching modes of the bidentate chelating CrO₄ ^2– ligand and of the Cr₂O₇ ^2– counterion.     

Synthesis and structure of (NH4)3[UO2(C3H2O4)2(NCS)] · 2H2O

Malonate-thiocyanate complex (NH₄)₃[UO₂(C₃H₂O₄)₂(NCS)] · 2H₂O is synthesized and studied by X-ray diffraction. The compound crystallizes in the monoclinic system: a = 13.9983(4) Å, b = 8.1947(2) Å, c = 16.4678(4) Å, β = 100.846(1)°, space group Cc, Z = 4, and R = 0.0158. The main structural units of the crystal are mononuclear [UO₂(C₃H₂O₄)₂(NCS)]^3? groups belonging to the AB ₂ ⁰¹ M ₁ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , B ⁰¹ = C₃H₂O ₄ ^2? , M ¹ = NCS^?). Discrete uranium-containing groups are connected by electrostatic interactions with ammonium ions and by hydrogen bonds. Some specific structural features of crystals containing [UO₂(L)₂(NCS)]^3? complexes, where L is the oxalate or malonate ion, are discussed.     

Synthesis of [Mn(O2CCH2CH2CO2)(2,2′-bipyridyl) (H2O)2]n·H2O

The title compound exists as a 1D coordination polymer consisting of succinate anions, manganese cations and 2,2-bipyridyl molecules. Twelve water molecules are present in the unit cell and are part of a hydrogen bonding system. Some of these waters are binding to manganese cations while others are only participating in hydrogen bonding. The structure has a monoclinic space group P2₁/c with a = 8.2750(3) Å, b = 11.5104(3) Å and c = 16.9113(6) Å, = 95.2727(16); V = 1603.96(9) ų and Z = 4.     

Synthesis and structural characterization of [Co(tren)(Tsal)]ClO4·H2O and [Ni(pn)(py)2(NCS)2]

Complexes [Co(tren)(Tsal)]ClO₄·H₂O 1 and [Ni(pn)(py)₂(NCS)₂] 2, (tren = tris(2-aminoethyl)amine, Tsal = thiosalicylate ion, pn = 1, 2-diamino propane and py = pyridine) have been synthesized and structurally characterized. Both complexes crystallize in the monoclinic space group C2/c with a = 21.3340(6), b = 11.7754(2), c = 14.8076(5) Å, = 100.3831(10)°, Z = 8 (1), and a = 7.2573(8), b = 17.8810(11), c = 15.2681(12) Å, = 101.170(2)°, Z = 4 (2). The metal atoms in both cases have distorted octahedral geometry. In 1, the tren ligand is quadridentate and Tsal is bidentate chelate. In 2, the pn ligand forms a bidentate chelate with the NCS ligands in trans positions. Complex 1 is diamagnetic whereas 2 shows paramagnetism with a magnetic moment of 3.10 B. M.     

Synthesis and crystal structure of [Cu(azpy)(H2O)4][Cu2(nta)2(azpy)]····6H2O: A two-dimensional network solid

The copper(II) complex [Cu(azpy)(H₂O)₄][Cu₂(nta)₂(azpy)]····6H₂O (nta = nitrilotriacetate, azpy = 4,4-azobispyridine) has been synthesized and structurally characterized. It crystallizes in the triclinic space group P , a = 8.6985(3) Å, b = 9.4776(3) Å, c = 14.6544(5) Å, = 71.5360(10)°, = 85.7600(10)°, = 88.1420(10)°, V = 1142.74(7) ų, Z = 1. The crystal structure consists of one-dimensional linear chain cations and dimeric anions. The copper centers in the anion possess distorted trigonal bipyramidal geometry, while Cu(2) has a distorted octahedral geometry in the cation. Coordinated water molecules in the one-dimensional chain form interionic hydrogen bonds with the oxygen atoms of the carboxylate of nta of the dimmer anion. These hydrogen bonds result in the formation of a two-dimensional network.     

Crystal structure of strontium aqua(ethylenediaminetetraacetato)cobaltate(II) tetrahydrate Sr[CoEdta(H2O)] · 4H2O

The complex Sr[Co^II Edta] · 5H₂O (I) (where Edta ^4? is the ethylenediaminetetraacetate ion) has been synthesized. The crystal structure of this compound is determined by X-ray diffraction. Crystals are monoclinic, a = 7.906(2) Å, b = 12.768(2) Å, c = 18.254(3) Å, β = 95.30(3)°, V = 1834.8 ų, space group P2₁/n, Z = 4, and R = 0.036. The structure is built up of the binuclear complex fragments {Sr(H₂O)₃[CoEdta(H₂O)]}, which consist of the anionic [CoEdta(H₂O)]^2? and cationic [Sr(H₂O)₃]²⁺ units linked by the Sr-O bonds into a three-dimensional framework. The coordination polyhedra of the Co and Sr atoms are mono-and bicapped trigonal prisms. The coordination sphere of the Co atom (the coordination number is equal to 6 + 1) involves six donor atoms (2N and 4O) of the Edta ^4? ligand and the O_w atom of water molecule. One of the Co-O distances (2.718 Å) is considerably longer than the other Co-O_lig distances (2.092–2.190 Å) and the Co-O_w(1) distance (2.079 Å). The Sr coordination polyhedron (the coordination number is eight) contains three water molecules, three carbonyl O atoms of the three different anionic complexes, and two O atoms of one acetate group of the fourth anionic complex. The Sr-O distances fall in the range 2.535–2.674 Å. The structural formula of the compound is {Sr(H₂O)₃[CoEdta(H₂O)]}_3∞ · H₂O.     

Crystal structure of triaquamaleatostrontium(II) monohydrate, [Sr(C4H2O4)(OH2)3]·H2O

[Sr(C₄H₂O₄)(OH₂)₃]·H₂O is monoclinic, P2₁/n, witha=11.476(2),b=7.027(1),c=12.344(2) Å, =115.74(3)°,V=896.67 ų,Z=4. The Sr atom is surrounded by nine oxygen atoms which come from four different maleate anions and three water molecules. The Sr–O distances range from 2.546(2) to 2.808(2) Å. The C–O distances are equal within the standard deviation 1.263(3) to 1.258(3) Å). In the maleate anion, the planes that contain the carboxylate groups form an angle of 74.44(9)°. Both carboxylate groups deviate significantly from planarity. The different coordination modes of the carboxylate group and the extensive hydrogen bonding present are responsible for the polymeric nature of the structure.     

水热合成三维超分子配位聚合物[Cd(C2O4)(H2O)2]·H2O及晶体结构

在水热条件下,制备了二维层状配位聚合物 [Cd(C2O4)(H2O)2] ·H2O(1)的单晶体,对其进行了X射线粉末衍射、元素分析、红外光谱、热重分析和X射线单晶衍射测定.单晶结构分析表明,该晶体属于三斜晶系,P-1空间群,晶胞参数a=0.60109(12)nm, b=0.66607(13)nm,c=0.84987(17)nm,α=74.72(3)°,β=74.33(3)°,γ=81.07(3)°,V=0.31473(11)nm3,Z=2,R1=0.015,ωR2=0.0368.草酸镉单晶结构由两个2D层构成,每一个2D层是由[Cd2(C2O4)2(H2O)4]·2H2O的重复单元形成,每个单元是由一个七配位独立镉原子配位而成(五个草酸氧原子和两个水分子氧原子).2D层与层之间通过不同层草酸分子与配位水分子之间及草酸与客体水分子之间形成的氢键将2D层状化合物连成一个3D超分子结构.热重分析表明该配位聚合物在340℃下稳定.     

Six-coordinated zinc complexes: [Zn(H2O)4(phen)] (NO3)2·H2O and [ZnNO3(H2O)(bipy)(Him)]NO3 (phen = 1,10-phenanthroline, bipy = 2,2′-bipyridine, and Him = imidazole)

Two novel six-coordinated zinc complexes, tetra-aqua(1,10-phenanthroline)zinc dinitrate monohydrate, [Zn(H₂O)₄(phen)](NO₃)₂·H₂O (1) and aqua(2,2-bipyridine)(imidazole)-nitratozinc nitrate, [ZnNO₃(H₂O)(bipy)(Him)]NO₃ (2) were prepared. Compound 1 crystallizes in the monoclinic space group P2₁/c with a = 8.780(4), b = 13.609(4), c = 15.368(5) Å, = 93.86(2)°C, V = 1832.1(12) ų. In 1, a phenanthroline molecule chelates the zinc atom and four water molecules complete the octahedral geometry around the metal. Compound 2 crystallizes in the monoclinic space group P2₁/n with a = 7.250(1), b = 24.554(4), c = 10.258(2) Å, = 107.880(10)°, V = 1737.9(5) ų. In 2, a bipyridine molecule and a nitrate anion chelate the zinc atom. An imidazole molecule and a water molecule then complete the six-coordinated geometry around zinc. The intermolecular packing is controlled by hydrogen bonding, especially in 1 and by stacking. The thermal stability of the compounds and the loss of water molecules and ligands was monitored by a thermogravimetric study.     

二维锰(Ⅱ)配位聚合物[Mn2(bppc)4(H2O)]n·2nH2O的合成、晶体结构及热稳定性研究

以2,6-双(2-吡嗪基)吡啶-4-对苯甲酸和MnCl2为原料,在水热条件下合成了二维锰(Ⅱ)配位聚合物[Mn2(bppc)4(H2O)]n·2nH2O,并用元素分析、红外光谱、X射线单晶衍射对此配位聚合物进行了表征,测定结果表明,晶体属于单斜晶系,P2(1)/c空间群,晶胞参数为:a=10.3918(9) nm, b=24.519(2) nm ,c=7.0140(6) nm,α=90°,β=105.0890(10)°,γ=90°.此配位聚合物中MnII之间通过配体中吡嗪环上的氮和羧基氧的桥连形成一维链状结构,一维链再通过羧基基团上的氧的进一步桥连形成二维结构.另外,热重分析表明,此配位聚合物具有较好的热力学稳定性.     

晶态配合物荧光材料[Ni(3,5-(SO3)2 CatH2)(phen)2(H2O)]·4H2O的合成、结构及性质

利用缓慢蒸发溶剂法合成了单核镍(Ⅱ)配合物[Ni(3,5-(So3)2CatH2)(phen)2(H2O)]·4H2O(CatH2=1,2-二羟基苯,phen=1,10-邻菲罗啉).利用X-射线单晶衍射、元素分析、红外光谱、热重分析和荧光光谱等对其进行了表征.结果表明,该配合物属于三斜晶系,P1空间群.镍离子与一个1,2-二羟基苯-3,5-二磺酸根离子、两个1, 1O-邻菲罗啉配体和一个水分子配位,形成[Ni(3,5-(SO3)2CatH2)(phen)2(H2 O)]结构.在结构单元中,还有四个未配位的水分子.未配位的水分子和[Ni(3,5-(SO3)2CatH2)(phen)2(H2 O)]结构通过O-H…O氢键相连,形成三维网状结构.与配体相比,配合物的荧光发射谱发生红移,发射峰在645 nm.荧光寿命为1.07 ns.     

Synthesis and crystal structure of [Co(phen)(H2O)4](SO4)⋅2(H2O)

The title complex, [Co(phen)(H₂O)₄](SO₄)2(H₂O) (phen = 1,10-phenanthroline) was prepared in aqua tert-butylperoxohydrogen solution. X-ray single crystal structure determination reveals that the complex consists of a phenanthrolinatocobalt(II)tetrahydrate dication, two uncoordinated water molecules and a sulfate anion. It crystallizes in the orthorhombic space group Pbca with a = 8.856(1), b = 18.318(3), c =21.918(5) Å, V = 3555.6(11) ų. The coordination geometry at each cobalt(II) atom is a slightly distorted octahedron.     

Crystal and molecular structure of four copper(II) ethylenediaminedisuccinates, [Cu2(RR,SS-Edds)] · 6H2O, Ba2[Cu(RR,SS-Edds)](ClO4)2 · 8H2O, Ba[Cu(SS-HEdds)]ClO4 · 2H2O, and Ba3[Cu2(RR,SS-Edds)2](ClO4)2 · 6H2O

Four Cu(II) complexes with the RR,SS-Edds ^4? and SS-HEdds ^3? anions are synthesized, and their crystal structures are studied. In the compounds [Cu2(RR,SS-Edds)] · 6H₂O (I) and Ba2[Cu(RR,SS-Edds)](ClO₄)₂ · 8H₂O (II), the ligand forms hexacoordinate chelate [Cu(Edds)]^2? complexes with the N atoms and O atoms of the propionate groups in the equatorial positions and the O atoms of the acetate groups in the axial vertices. In the compounds Ba[Cu(SS-HEdds)]ClO₄ · 2H₂O (III) and Ba3[Cu2(RR,SS-Edds)₂](ClO₄)₂ · 6H₂O (IV), one of the propionate arms, the protonated arm in III and the deprotonated arm in IV, does not enter into the coordination sphere of the Cu atom. An acetate arm moves to its position in the equatorial plane, and the free axial vertex is occupied by an O atom of the perchlorate ion. In I–IV, the lengths of the equatorial Cu-N and Cu-O bonds fall in the ranges 1.970–2.014 and 1.921–1.970 Å, respectively. The axial Cu-O bonds with the acetate groups and ClO ₄ ^? anions are elongated to 2.293–2.500 and 2.727–2.992 Å, respectively. In structure I, the second Cu atom acts as a counterion forming bonds with the O atoms of two water molecules and three O atoms of the Edds ligands. In II–IV, the Ba²⁺ cations are hydrated and bound to the O atoms of the anionic complexes and (except for one of the cations in IV) ClO ₄ ^? anions. The coordination number of the Ba cations is nine. The structural units in I–IV are connected into layers. In I, an extended system of hydrogen bonds links the layers into a framework. In II and III, the layers are linked only by weak hydrogen bonds, one bond per structural unit. In IV, ClO ₄ ^? anions are bound to the Ba and Cu atoms of neighboring layers, thus serving as bridges between the layers.     

Synthesis and crystal structure of a new bimetallic complex of diethylenetriamine pentaacetic acid: [YbAg2(dtpa)(H2O)]·3H2O

The reaction between Yb(III) nitrate, Ag(I) nitrate, and the diethylenetriamine pentaacetate (dtpa) ligand gives rise to a bimetallic complex. [YbAg₂(dtpa)(H₂O)]·3H₂O is triclinic, space group P-1, with a = 8.768 (3), b = 9.862 (2), c = 13.055 (2) Å, = 75.40 (1), = 83.00 (2) and = 87.46 (2)°. Each dtpa is coordinated to one ytterbium and six silver atoms. The resulting crystal structure can be described as 2D packing. In the layers, the ytterbium atoms are connected through [Ag(COO)]₂ dimers. Strong hydrogen bonds, involving the noncoordinated water molecules, ensure crystal cohesion.     

Crystal structure of [Co(Ox)(NH3)4][Bi(Edta)] ⋅ 3H2O

The crystal structure of [Co(Ox)(NH₃)₄][Bi(Edta)] ? 3H₂O is determined. The crystals are monoclinic, a = 9.291 Å, b = 22.275 Å, c = 11.402 Å, β = 105.79°, V = 2270.7 ų, Z = 4, and space group P2₁/c. The [Bi(Edta)]^? anionic complexes are linked into polymeric chains through two Bi-O bonds with the neighboring complexes.