含有双螺旋链的配位聚合物[Co(dpa)prz0.5]n的合成、晶体结构及磁性质

A coordination polymer [Co(dpa)prz_0.5]_n(1) with double-helix chains has been constructed hydrothermally using H₂dpa (H₂dpa=diphenic acid), prz (prz=piperazine) and Co(NO₃)₂·6H₂O. The structure and magnetic properties of the complex were investigated. The complex crystallizes in triclinic system and P1 space group. Each Co atom is five-coordinated and takes a distorted tetragonal pyramid geometry. Two carboxylates of the H₂dpa ligands bridge four Co(Ⅱ) ions to form infinite right-handed or left-handed helical -C-O-Co- chains. The two types of helical chains are interconnected to each other through the Co(Ⅱ) centers to produce double-helix chains. The chains form a 2D sheet through the coordination interaction of prz molecules between adjacent chains. The sheets are further interlinked by hydrogen bond interactions to generate 3D coordination frameworks. Magnetic studies for complex 1 show stronger antiferromagnetic coupling between the Co(Ⅱ) ions. CCDC: 709275.     

邻苯二甲酸单乙酯铜配合物的晶体结构与强反铁磁性

A hydrated tetra-carboxylato-bridged dinuclear copper(Ⅱ) complex [Cu₂(mEP)₂(H₂O)₂]₂ (1) (mEp is mono -ethyl phthalate or 1,2-benzenedicarboxylate monoethyl ester) has been prepared and characterized by X-ray diffraction single crystal structure analysis and magnetic measurements. This dinuclear complex adopts dimeric paddle-wheel cage structure and the coordination model around each copper(Ⅱ) atom is square-pyramidal with four oxygen atoms of the carboxylate groups from four different mono-ethyl phthalate ligands and one oxygen atom of water as apical position. The magnetic data for 1 exhibited strong intramolecular antiferromagnetic interaction between the two paramagnetic metal ions with 2J=-315.18 cm^-1. Comparing with other related complexes in structure and magnetic propertity, the main factor which determines the strong antiferromagnetic interaction in the dimeric copper(Ⅱ) carboxylates is the electronic structure of the bridging O-C-O moiety. CCDC: 624561.     

配合物[Cu(HPHAc)2(py)2](H2PHAc=苯羟乙酸，py=吡啶)的合成和晶体结构

The novel copper(Ⅱ) complex with α-hydroxyphenylacetic acid (H₂PHAc) and pyridine (py) ligands, [Cu(HPHAc)₂(py)₂], has been synthesized and characterized by elemental analysis and IR spectroscopy. Its crystal structure was determined by single crystal X-ray diffraction techniques. The crystal belongs to monoclinic with space group C2/c. The cell parameters are: a=1.712 5(3) nm, b=1.533 2(2) nm, c=0.963 42(14) nm, β=111.866(2)°, V=2.347 6(6) nm³, and D_c=1.483 Mg·m^-3, Z=4, F(000)=1 084. The structure was refined to final R₁=0.071 4, wR₂=0.166 1. The complex has a six-coordinated distorted octahedral geometry, in which copper(Ⅱ) ion coordinates with two carboxylic oxygen atoms and two hydroxyl oxygen atoms from the two α-hydroxyphenylacetic acid ligands, two nitrogen atoms from the two pyridine ligands. The analysis of the crystal structure indicates that the complex has a one-dimensional chain structure, which is formed by intermolecular hydrogen bonds. CCDC: 255346.     

苯甲醛缩三乙烯四胺Schiff碱Co(Ⅱ)配合物固相合成及氧合性能研究

Three new cobalt complexes were synthesized by solid-state reaction at room temperature. It was found that one mole of complex reacted with two moles of oxygen at room temperature. And the oxygenated complexes [Co·(L₁)₂·2O₂](NO₃)₂·2H₂O (L₁=N,N′-bis(4-hydroxyl-3-methoxy-benzyl)-triethylenetetramine), [Co·(L₂)₂·2O₂](NO₃)₂ ·2H₂O (L₂=N,N′-bis(4-hydroxyl-benzyl)-triethylenetetramine) and [Co·L₃·2O₂](NO₃)₂·2H₂O (L₃=N,N′-bis(2-hydroxyl-benzyl)-triethylenetetramine) were obtained and characterized by elemental analysis, IR spectra, ¹H NMR, TG/DTA, UV-Vis and molar conductance. The coordinated oxygen contents in the oxygenated complex were also determined by weight method. It was found that one O₂ molecule coordinated to the Co ion and formed superoxo type oxygenated complex.     

银(Ⅰ)、锌(Ⅱ)与2，2′-(2-氨基-苯氧基)乙醚配合物的合成及晶体结构

The compound 2,2′-(2-amino-phenoxy)-ether[L] was synthesized from the reaction of diethylene glycol with tosyl chloride. AgClO₄ and ZnCl₂ each react with L to give two complexes [Ag₂L₂(H₂O)(ClO₄)₂] (1) and [ZnLCl₂]_n (2) respectively, and characterized by FTIR and single crystal X-ray diffraction. The results of structural analysis indicated that both complexes crystallize in the monoclinic system with space group P2₁/c. 1 is a dinuclear complex, and 2 forming 1D zigzag chain by Zn(Ⅱ) linking adjacent ligands in turn. When viewed from the top of the chain, the structure of 2 shows the unidimensional tube. CCDC: 748592, 1; 748594, 2.     

三元混合配合物Cu(C10H8N2O3)·(C5H5N)·(H2O)的合成和晶体结构

The novel copper(Ⅱ) complex with 2-oxo-propionic acid benzoyl hydrazone and pyridine ligands, Cu(C₁₀H₈N₂O₃)·(C₅H₅N)·(H₂O) (C₁₀H₈N₂O₃^2- is the dinegative ion of 2-oxo-propionicacid benzoyl hydrazone), has been synthesized and characterized by elemental analysis and IR. The crystal structure of the title complex was determined by single crystal X-ray diffraction technique. Complex crystallized in the triclinic space group P1 with a = 0.729 08(10) nm, b= 1.020 01(14) nm, c= 1.126 28(15) nm, α = 71.644(2) °, β = 80.437(2) °, γ = 89.160(2)°, V= 0.78328(18) nm³, Z= 2, D_c= 1.547 Mg·m^-3, μ(MoKα) = 1.417 mm^-1, F(000) = 374. The final R₁ = 0.030 6, wR₂= 0.084 2 for 2 992 observed reflections [I≥2σ(I)] out of 3357 unique reflections. In this complex, copper(Ⅱ) ion is square-pyramidally coordinated by two oxygen atoms and one nitrogen atom of tridentate C₁₀H₈N₂O₃^2- ligand, one nitrogen atom of the pyridine ligand, and one oxygen atom of water molecule with the oxygen atom of water molecule locating at the apical position. The analysis of the crystal structure indicates that the complex has a one-dimensional chain structure, which is formed by intermolecular hydrogen bonds. CCDC: 222656.     

含N4O2配体的铁(Ⅱ)配合物的合成、结构及催化烷烃氧化反应

Two iron(Ⅱ) complexes [Fe(tpdoen)](FeCl₄)Cl (2, tpdoen=N,N-bis(2-pyridylmethoxyethyl)-N-(2-pyridylmethyl)amine) and [Fe(tpdoen)](ClO₄)₂ (3) with an N₄O₂ ligand containing two potentially π-coordinate oxygen atoms were synthesized as functional models of non-heme iron oxygenases. The X-ray crystal structure analysis corroborated that complex 3 possesses a significantly distorted six-coordinate pseudooctahedral configuration, in which all six heteroatoms (N₄O₂) coordinate to the iron center. The catalytic property of complex 3 for alkane oxidation were explored using H₂O₂, TBHP and mCPBA as oxidants in the presence of excess substrates under mild conditions. When cyclohexane oxidation process was monitored by UV-Vis spectra using H₂O₂ as oxidant at 0 ℃, a short-life band appeared at ca. 550 nm, which is attributed to the in-situ Fe(Ⅲ)-OOH species. CCDC: 607630.     

顺式-二(硫氰酸根)·二氨合铂(Ⅱ)的合成、表征及其水溶液析出物质机制的探讨

Cis-diaminedithiocyanatoplatinum(Ⅱ) (cis-[Pt(SCN)₂(NH₃)₂]) was prepared and characterized through content analysis of Pt, MS, IR. The results show that the complex has cis configuration and the bond type of Pt and SCN^- is Pt-S. When the aqueous solution of the complex was stored for one week, an orange-yellow precipitation appeared, different from the complex with light yellow color. Further comparative studies of these two complexes suggested that the precipitation is cis-[Pt(NCS)₂(NH₃)₂], the linkage isomerism of cis-[Pt(SCN)₂(NH₃)₂]. The mechanism of the isomerism reaction is also discussed.     

氰根桥连的锰钴五核配合物的合成与晶体结构

Reaction of [Mn(bpm)₂]²⁺ with K₃[Co(CN)₅(NO)] produces a cyano-bridged bimetallic compound,{[Mn(bpm)₂]_1.5[Co(CN)₅(NO)]}·2H₂O (1), (bpm=bis(1-pyrazol)methane). Compound 1 crystallizes in the tetragonal space group P4₃2₁2 with a=1.305 08(8) nm, b=1.305 08(8) nm, c=4.386 7(5) nm, V=7.471 5(10) nm³, and Z=8. Complex 1 exhibited a structure of a pentanuclear cluster. The Mn²⁺ ions each are surrounded by bpm ligands, forming the [Mn(bpm)₂]²⁺ cation fragment. Three cation fragments are connected to the two anion fragments, [Co(CN)₅(NO)]^3-, by cyanide bridges. The five metal ions form a trigonal bipyramidal structure, where the Mn²⁺ ions are situated in the equatorial plane and the Co²⁺ ions are on both sides of the plane. As a semirigid ligand, bpm is more flexible than rigid 2,2′-bipydine, and it results in the two different configurations in the [Mn(bpm)₂]²⁺ cation fragment. CCDC: 635764.     

Co[(C6H11O)2PS2]2·2Py的合成和晶体结构

Oxidation process of Co[(C₆H₁₁O)₂PS₂]₂ and substitute-reduction reaction of Co[(C₆H₁₁O)₂PS₂]₃ with pyridine have been studied by spectrophotometric methods, respectively. The equilibrium constant was found to be K=0.63±0.02(mol·dm^-3)^-3. The crystal structure of Co[(C₆H₁₁O)₂PS₂]₂·2Py has been determined by X-ray diff- raction method. The crystal belongs to triclinic system, space group P1, with cell parameters: a=6.944(2)?,b=9.277(3)?,c=15.981(6)?,α=91.79(3)°,β=99.55(3)°,γ=94.44(3)°,V=1011.2(6)?³,Z=2,M_r=803.94,D_c=1.320Mg·m^-3,F(000)=425,μ=0.747mm^-1,final R=0.0700 and wR=0.1988 for 3626 re-flections with I≥2σ(I). The cobalt atom in the title complex has a octahedral geometry with four Co-S bonds and two Co-N bonds. The central atom P is tetrahedrally surrounded by two sulphur atoms and two oxygen atoms in the dicyclohexyldithiophosphate ligand. The six carbon atoms of cyclohexyl take the chair conformation.     

配合物[Tb(p-ClBA)3(phen)]2的结构和性能

Terbium p-chlorobenzoate complex with 1,10-phenanthroline, [Tb(p-ClBA)₃(phen)]₂(1) has been obtained in the ethanol solution, where p-ClBA=p-chlorobenzoate and phen=1,10-phenanthroline. It crystallizes in the triclinic system, space group P1, a=1.008 1(2) nm, b=1.185 7(2) nm, c=1.431 1(3) nm, α=110.826(4)°, β=96.436(4)°, γ=101.737(4)°, Z=2. The two Tb(III) ions are linked by four carboxylate groups through their bidentate bridging modes, forming a dimeric unit with crystallographic inversion center. Each terbium ion has an eight-coordinate geometry with four of the coordination sites occupied by four oxygen atoms from the four bridging carboxylates, respectively, two oxygen atoms from bidentate carboxylate, and the remaining positions occupied by two nitrogen atoms from a 1,10-phenanthroline molecule. The Tb(III) ion adopt a distorted square antiprism coordination geometry. The excitation and luminescence data observed at room temperature show that the title complex emits very intensive green fluorescence under ultraviolet light. The result of thermal analysis indicates the complex [Tb(p-ClBA)₃(phen)]₂ is quite stable to heat. CCDC: 221921.     

从配位聚合物到单分子化合物的转化：Demko-Sharpless四唑合成法制备两个新颖的Co(II)配合物

The reaction of CoCl₂·6H₂O with 4-cyanopyridine N-oxide in the present of NaN₃ affords two novel complexes, {[(POTZ)(H₂O)₂N₃]Co(H₂O)} (1) and Co(POTZ)₂(H₂O)₄ (2) (POTZ=4-tetrazolyl pyridine N-oxide), which are two different phases yielded at different stages of a single Demko-Sharpless′ tetrazole synthesis reaction. Surprisingly the 1D chain coordination polymer 1 is almost completely converted into monomeric complex 2 in this reaction, and, in a separate test, 2 also can be converted into 1. CCDC: 641222, 1; 641223, 2.     

N，N′-双(4-甲基-2-苯并噻唑基)-2，6-吡啶二酰胺钴(Ⅱ)配合物的合成和晶体结构(英)

Treatment of deprotonated N，N′-bis(4-methyl-2-benzothiazolyl)-2, 6-pyridicarboxamide (L^2-) with CoCl2·6H2O yields the mononuclear complex, (Et₄N)₂[CoL₂]·0.5H₂O. Single crystal X-ray structural determination has been carried out for the complex, crystal system: Monoclinic, space group: P2₁/c, a=1.444(1) nm, b=1.969(1) nm, c=2.448(1) nm, β=118.02(1)°, V=6.143 0(15) nm³, Z=4. In this complex, the central Co(Ⅱ) atom is in an octahedron environment, with four deprotonated amide-N atoms in the equatorial plane and two pyridine-N atoms in the axial positions. CCDC: 252558.     

Heterometallic (ZrIII)2—Al hydrides [(Cp2Zr)2(μ-H)](μ-H)2AlX2 (X = Cl or Br): preparative synthesis and reactivity. Molecular structure of [(Cp2Zr)2(μ-Cl)](μ-H)2AlCl2

A procedure was developed for the synthesis of trinuclear cyclic (Zr^III)₂—Al hydrides [(Cp₂Zr)₂(μ-H)](μ-H)₂AlX₂ (X = Cl (1a) or Br (1b)). These complexes were prepared in 60–65% yields by the reaction of Cp₂ZrX₂ with LiAlH₄ in the presence of CoBr₂ and tolane. The structures of complexes 1a and 1b and iodide 1c (X = I) were studied by NMR spectroscopy in solvents of different basicities (toluene, THF, and pyridine). Complex 1a is unsolvated and monomeric in all solvents; complex 1b, in toluene and THF; complex 1c, in toluene only. At room temperature, complex 1a does not catalyze hydrogenation of hex-1-ene and does not react with tolane, but reacts with the latter at high temperature to give bis(η⁵-cyclopentadienyl)-2,3,4,5-tetraphenylzirconacyclopentadiene. The reaction of equivalent amounts of complex 1a and HCl produces the [(Cp₂Zr)₂(μ-Cl)](μ-H)₂AlCl₂ complex. The structure of the latter was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2418–2423, November, 2005.     

共平面的μ-S桥联（1，10-菲咯啉）钯(Ⅱ)双核配合物的晶体结构与π-π堆积

A novel μ-S-bridged di-palladium(Ⅱ) complex, {[(phen)Pd( μ-SPr)₂Pd(phen)](NO₃)₂·2H₂O} (1) was synthesized and characterized by the ¹H NMR, element analysis and single crystal X-ray diffraction. It crystallizes in the monoclinic space group C2/c with unit cell parameters: a=2.165 1(3) nm, b=1.291 4(2) nm, c=2.716 2(3) nm, β=111.987(3)°, and V=7.041 8(16) nm³, Z=8, R=0.054 4, wR=0.127 4. The X-ray crystal structure analysis revealed that two 1,10-phenanthroline palladium(Ⅱ) moieties were bridged by two n-propylmercapatan molecules in coplanar fashion with the dimensions of 1.55 nm×0.88 nm. The plane-to-plane distance of the complex 1 is 0.33 nm, which reveals strong aromatic-aromatic π-π interaction. CCDC: 292998.     

Crystal and molecular structure and properties of [Ni(4-NH2Py)2(iso-Bu2PS2)2] and [Co(4-NH2Py)(iso-Bu2PS2)2]

The interaction of the Co(iso-Bu₂PS₂)₂ chelate with 4-NH₂Py afforded a paramagnetic complex [Co(4-NH₂Py)(iso-Bu₂PS₂)₂] (μ_eff = 4.53 BM). Single crystals of [Ni(4-NH₂Py)₂(iso-Bu₂PS₂)₂] (I) and [Co(4-NH₂Py)(iso-Bu₂PS₂)₂] (II) were grown and used for X-ray diffraction investigation (X8 APEX diffractometer, MoK _α radiation). Crystals I are monoclinic with unit cell parameters a = 12.5336(5) Å, b = 9.4356(4) Å, c = 16.4095(6) Å; β = 111.351(1)°; V = 1807.4(1) ų; Z = 2, ρ = 1.223 g/cm³, space group P2₁/n. Crystals II are triclinic with unit cell parameters a = 8.7572(4) Å, b = 9.6934(6) Å, c = 18.665(1) Å; α = 79.374(2)°, β = 87.049(2)°, γ = 75.640(2)°; V = 1508.6(1) ų; Z = 2, ρ = 1.259 g/cm³; space group . The structures of I and II are formed by isolated mononuclear molecules. The coordination unit is NiN₂S₄ (octahedron) in I and CoNS₄ (tetragonal pyramid) in II. The 4-NH₂Py molecule is coordinated through the N atom of the heterocycle. Electronic spectroscopy data for II agree with the symmetry of the NS₄ polyhedron found by X-ray diffraction (XRD) analysis. The noncoordinated amine groups link the complex molecules via N-H...S hydrogen bonds. __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 6, pp.1072–1080, November–December, 2005. Original Russian Text Copyright ? 2005 by T. E. Kokina, L. A. Glinskaya, E. A. Sankova, R. F. Klevtsova, and S. V. Larionov     

2,4,6-三甲基苯甲酸和1,10-邻菲啰啉双核铽配合物的合成和晶体结构

A binuclear terbium complex with 2,4,6-Trimethylbenzoate and 1,10-phenanthroline, [Tb₂(TMBA)₆(Phen)₂], has been synthesized (TMBA=2,4,6-Trimethylbenzoic acid and phen=1,10-phenanthroline) and characterized by IR, elemental analysis and X-ray diffraction methods. The title complex crystallizes in monoclinic system, space group P2₁/c with a=1.327 5(2) nm, b=2.817 9(5) nm, c=1.282 5(2) nm, β=116.692(3)°, V=4.286 2(13) nm³, Z=4，D_c=1.423 g·cm^-3. There are four bridged carboxylate groups of the 2,4,6-trimethylbenzoic acid bonded to the two terbium ions, each ions is also chelated with the two oxygen atoms of a molecule of the 2,4,6-trimethylbenzoic acid and the two nitrogen atoms of a 1,10-phenanthroline respectively, forming a 8-coordination distorted square antiprism. Average Tb-O and Tb-Ndistance of the two Tb(Ⅲ) ions are equal respectively. This shows the two terbium ions are in the same chemical enviorments. The complex emits intense green fluorescence under ultraviolet light. CCDC: 619215.     

Shiff碱茚(1，2-b)喹喔啉-11-酮缩氨基硫脲合钴(Ⅱ)配合物的合成、表征与晶体结构

The title complex [CoL₂](OH)Cl·1.1DMF (1) was synthesized (where L is Indene[1,2-b]Quinoxalin-11-Alkone Thiosemicarbazone) and characterized by elemental analysis, MS and X-ray single crystal structural analysis. The crystal structure 1 belongs to monoclinic system with space group C2/c, a=2.236 5(2) nm, b=1.990 4(2) nm, c=1.850 0(1) nm, β=116.576(2)°, V=7.365 2(9) nm³, Z=8. Each Co(Ⅱ) atom lies at the centre of a distorted coordination octahedron, formed by two L tridentate chelating ligands. The structure of the ligand L is nearly a plane. CCDC: 297352.     

氧桥双β-二亚胺钴配合物的合成及结构

Treatment of the lithium β-diketiminate [Li{N(R)C(NMe₂)C(H)C(NMe₂)N(R)}]₂ (1) (R=SiMe₃) with KOBu^t, KOH·H₂O and CoCl₂ in tetrahydrofuran gave in good yields the RO bridged β-diketiminato Co(Ⅱ) complex [Co{N(H)C(NMe₂)C(H)C(NMe₂)N(R)-( μ-OR)}]₂ (2) at ambient condition. The crystal data of (2) are as follows: crystal system, monoclinic; space group, P121/n1; a=0.963 9(3) nm, b=1.077 2(3) nm, c=2.025 0(6) nm, V=2.102 5(10) nm³, Z=2, D_c=1.186 g·cm^-3, F(000)=804, μ(Mo Kα)=0.934 mm^-1, R₁=0.047 8, wR₂=0.097 9. In solid state, complex (2) is a dimer bridged by RO (R=SiMe₃) group and the two Co²⁺ are in distorted tetrahedron. CCDC: 249253.     

铜配合物[CuL2Cl2]·4H2O的合成和晶体结构(L=3-乙基-4-对甲氧苯基-5-(2-吡啶基)-1，2，4-三氮唑)

A new copper(Ⅱ) complex, [CuL₂Cl₂]·4H₂O, [L=3-ethyl-4-(p-methoxyphenyl)-5-(2-pyridyl)-1,2,4-triazole], was synthesized and characterized by X-ray crystallography and infrared spectroscopy. The complex crystallizes in triclinic system with space group P1, a=0.843 9(7) nm, b=0.965 5(8) nm, c=1.093 6(8) nm, α=84.026(19)°, β=82.33(2)°, γ=89.167(19)°, V=0.878 3(12) nm³, Z=1 with final R=0.033 8. The copper atom lies in a distorted octah-edral environment with two bidentate chelating ligands(L) in the equatorial plane and two Cl^- ions in the axial positions. The ligand L coordinates via one triazole nitrogen and one pyridine nitrogen atom. The molecules are stabilized by intermolecular hydrogen bonds in the crystal lattice. CCDC: 705817.