A Michael-type reaction between acrylato ions and ethylenediamine coordinated to Ni(II). Synthesis,crystal structure and magnetic properties of [Ni2(EDDP)2(H2O)2] · 2H2O (H2EDDP = ethylenediamine-N,N-dipropionic acid)

The reaction between NiCO₃ · Ni(OH)₂, acrylic acid and ethylenediamine in a 2:4:1 molar ratio affords the binuclear complex, [Ni₂(EDDP)₂(H₂O)₂] · 2H₂O 1. The organic ligand, EDDP^2? (the dianion of the ethylenediamine-N,N-dipropionic acid ligand), results from the addition of one amine group to the carbon–carbon double bonds of two acrylato ions. The crystal structure of 1 consists of neutral centrosymmetric entities, with the nickel ions connected by two carboxylato groups, each one acting as a monoatomic bridge. The intramolecular Ni?Ni distance is 3.212 Å. The metal ions exhibit an octahedral geometry. The cryomagnetic investigation of 1 reveals an antiferromagnetic coupling of the nickel(II) ions (J = ?21.8 cm^?1, H = ?JS_Ni1S_Ni2).     

Hydrothermal synthesis,crystal structure and physical properties of {[Gd(H2O)4(μ2-C6NO2H5)2Gd(H2O)4](μ3-C6NO2H4)2(ZnCl3)2} · 2H2O · 2Cl

A bimetallic 4f–3d tetranuclear complex {[Gd(H₂O)₄(μ₂-C₆NO₂H₅)₂Gd(H₂O)₄](μ₃-C₆NO₂H₄)₂(ZnCl₃)₂} · 2H₂O · 2Cl (1) has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 is characterized by a tetranuclear Gd₂Zn₂ structure with the gadolinium and zinc atoms interconnected by isonicotinic acid ligands. The tetranuclear species of {[Gd(H₂O)₄(μ₂-C₆NO₂H₅)₂Gd(H₂O)₄](μ₃-C₆NO₂H₄)₂(ZnCl₃)₂} link to isolated chlorine ions and water molecules via π?π interactions and hydrogen bonds to yield a 3-D supramolecular framework. Photoluminescent investigation reveals that the title complex displays an emission in ultraviolet region. The solid-state diffuse reflectance spectra of 1 reveal the presence of a sharp optical gap of 3.66 eV.     

Synthesis and crystal structure of [nBu4N][Er(pic)4] · 5.5H2O: a new infrared emitter

The new erbium(III) complex of picolinic acid (Hpic), [ⁿBu₄N][Er(pic)₄] · 5.5H₂O, was synthesized and the crystal structure determined by single-crystal X-ray diffraction. The compound was further characterized using IR, Raman, ¹H NMR and elemental analysis. The picolinate ligands (pic⁻) are coordinated through N,O-chelation to the erbium cations, as shown by X-ray diffraction and spectroscopic results, leading to an eight coordinate complex. Photoluminescence measurements were performed for this compound which exhibits infrared emission.     

Synthesis,structure of a coordination polymer: {Na2[Zn(C2O4)1.5H2PO4] · 2H2O}n

A phosphatooxalate compound {Na₂[Zn(C₂O₄)_1.5H₂PO₄] · 2H₂O}_n 1 was synthesized under hydrothermal condition and characterized by single-crystal X-ray diffraction, IR spectroscopy, thermal gravimetric analysis (TGA) and fluorescent spectroscopy. X-ray single-crystal analysis revealed that its structure was a new mixed inorganic–organic ligand supramolecular framework building up through multilayer assembly.     

Organic–inorganic hybrid oxides: Structure and magnetic properties of [{Cu(terpy)}2Mo6O17(H2O)(O3PCH2NH2CH2PO3)2] · H2O,a bimetallic oxide constructed from novel {Mo6O17(H2O)(O3PCH2NH2CH2PO3)2}4− clusters

The hydrothermal reaction of MoO₃, CuSO₄ · 5H₂O, 2,2′:6′:2″-terpyridine (terpy) and bis-N,N-(methylphosphonic acid) amine (H₂O₃PCH₂NHCH₂PO₃H₂) provided blue crystals of the bimetallic oxide [{Cu(terpy)}₂Mo₆O₁₇(H₂O)(O₃PCH₂NH₂CH₂PO₃)₂] · H₂O (1 · H₂O). The three-dimensional structure of 1 is constructed from {Mo₆O₁₇(H₂O)(O₃PCH₂NH₂CH₂PO₃)₂}⁴⁻ clusters linked through {Cu(terpy)}²⁺ subunits. The cluster consists of three pairs of edge-sharing {MoO₆} octahedra linked through corner-sharing interactions into a {Mo₆O₆} ring. One phosphonate ligand spans the diameter of the ring, bridging four molybdenum sites and leaving at a pendant {PO} group at each terminus. The second diphosphonate ligand exploits one {–PO₃} unit to cap the hexamolybdate ring and bridge all six molybdenum sites while the second {–PO₃} terminus bridges two molybdenum sites, leaving a pendant {PO} unit. Crystal data: C₃₄H₄₅Cu₂Mo₆N₈O₃₅P₄: monoclinic, P2₁/n, a = 11.9431(7) Å, b = 17.382(1) Å, c = 27.524(2) Å, β = 90.429(1)°, V = 5713.7(6) Å³, Z = 4, D_calc = 2.270 g cm⁻³, R₁ = 0.0466.     

Hydrothermal synthesis, crystal structure and properties of complex [Co (odpa) (phen) 2 ( H2O )] · H2O

以4,4’-氧化二苯四羧酸二酐和1,10-邻菲啰啉为配体在水热条件下合成了标题配合物,并用元素分析、红外光谱、X-射线单晶衍射以及热重分析对配合物进行了表征.晶体结构分析表明配合物为三斜晶系,P-1空间群a=11.190(2)(A),b=12.587(2) (A),c=13.097(3)(A),α=102.688(3)°,β=105.751(2)°,γ =92.615(2)°,V =1721.1(6)A3,Z=2.配合物为单核结构,相邻的单核分子通过氢键的识别作用形成一维超分子双链.π…π堆积作用和C-H…π之间弱相互作用将邻近超分子双链的进一步扩展为三维超分子结构.     

Divalent metal complexes of formylhydrazine: Syntheses and crystal structures of M(CH4N2O)2(H2O)2·2NO3 (M = Zn,Co)

The syntheses and crystal structures of Zn(CH₄N₂O)₂(H₂O)₂·2(NO₃) (1) and Co(CH₄N₂O)₂(H₂O)₂·2(NO₃) (2), the first well-characterised metal complexes of formylhydrazine (fh), are described. In both compounds, the fh acts as an N,O-bidentate ligand in a centrosymmetric [M(fh)₂(H₂O)₂]²⁺ cation, with charge balance supplied by nitrate counter ions. The packing for the two compounds are quite different: in 1, chains of [Zn(fh)₂(H₂O)₂]²⁺ units are seen in the triclinic unit cell, whereas in the monoclinic structure of 2, sheets of cations occur. This might arise because the conformations of the five-membered chelate rings for the ligands are slightly different, with that for 2 showing a greater degree of puckering.     

Synthesis,crystal structure,and thermal stability of a novel 3D cadmium carboxyphosphonate containing left-hand helical chains Cd3Cl2[(O3PCH2–N(H)C5H9–COO)2(H2O)2] · 4H2O

A novel 3D cadmium carboxyphosphonate containing left-hand helical chains, Cd₃Cl₂[(O₃PCH₂–N(H)C₅H₉–COO)₂(H₂O)₂] · 4H₂O 1 has been synthesized by hydrothermal reaction at 120 °C and structurally characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. In compound 1, the hexanuclear clusters based on Cd(1)O₄Cl₂, Cd(2)O₄Cl₂, Cd(3)O₆ and CPO₃ polyhedra are interconnected through carboxyphosphonate ligands to form a 3D open-framework structure with channel system. The result of connections in this manner is the formation of 20- and 30-atom rings that are parallel to one another and run in the a-axis direction. It is interesting that a type of left-hand helical chain is formed by HL^2? ligands bridging Cd₃ ions running along the b-axis.     

配合物[Cd(na)2(phen)2]·[Cd(na)2(phen)2]·3H2O的合成、晶体结构及荧光性质

用硝酸镉与1-萘甲酸、邻菲罗啉水热合成了配合物[Cd(na)2(phen)2]·[Cd(na)2(phen)2]·3H2O (Hna=1-萘甲酸,phen=1,10-邻菲罗啉),并用X-射线单晶衍射、红外、热重和元素分析进行了结构表征.结果表明,该配合物属三斜晶系,P-1空间群,晶胞参数为:a=1.27123(16) nm,b=1.6369(4) nm,c=1.9656(2)nm,α=75.613(2)°,β=84.363(2)°,γ=71.5380(10)°,Z=2,V=3.7572(8) nm3.配合物包含两个离散的单核[Cd(na)2(phen)2]子单元和三个结晶水分子,并通过分子间氢键形成三维超分子结构.在335 nm的紫外光激发下,配合物发射出源于Na-之间电子跃迁的荧光.     

Single crystal structure of a two-dimensional framework: [{Co(4,4′-bpy)(HO3PCH2CH2CH2CH2PO3H)(H2O)2}·4H2O]n

The structure of [{Co(4,4^′-bpy)(HO₃PCH₂CH₂CH₂CH₂PO₃H)(H₂O)₂}·4H₂O]_n 1 was determined by single crystal X-ray diffraction. Compound 1 contains a new two-dimensional framework layer, which is built up from parallelogram units in bc plane. The layers are constructed into a three-dimensional structure by interlayer hydrogen bonds.     

Synthesis,crystal structure and magnetic properties of one-dimensional cyano-bridged bimetallic complex of [Mn(Me2-bipy)2]3[W(CN)8]2·9H2O

An octacyanotungstate(V)-manganese(II) bimetallic assembly [Mn(Me₂-bipy)₂]₃[W(CN)₈]₂·9H₂O (1) (Me₂-bipy = 4,4′-dimethyl-2,2′-bipyridine) was synthesized in methanol and characterized by X-ray crystallography. X-ray analysis shows that complex 1 is a neutral, one-dimensional (1D) infinite chain polymer. Magnetic data analysis demonstrates a long-range magnetic interaction and two different antiferromagnetic coupling constants obtained by fitting between Mn and W ions in 1.     

The first metal chelate of un-substituted 2,6-pyridine-dicarboxamide (pdcam): synthesis,molecular and crystal structure,and properties of [CuII(pdc)(pdcam)] · 2H2O (pdc = 2,6-pyridine-dicarboxylato(2−) ligand)

The compound (2,6-pyridine-dicarboxamide)(2,6-pyridine-dicarboxylato)copper(II) dihydrate ([Cu(pdc)(pdcam)] · 2H₂O, compound 1) has been synthesised by reaction of Cu₂(CO₃)(OH)₂, H₂pdc acid and pdcam in an aqueous-ethanol medium. The new compound has been characterised by thermal, spectral, magnetic and X-ray diffraction methods. Its crystal consists of a 3D hydrogen bonded network where all N–H(amide) bonds of pdcam act as H-donors for O carboxyl(pdc) or water acceptor atoms. The Cu(II) atom exhibits an elongated octahedral coordination, type 4 + 2. Both pdc and pdcam ligands define a nearly orthogonal dihedral angle (88.4°). The anionic pdc acts as mer-NO₂(equatorial) tridentate ligand, supplying three among the four closest to the metal donor atoms (Cu–N 1.913(2), Cu–O 2.022(2) and 2.055(2) Å). The diamide pdcam ligand displays a mer-N(equatorial) + O₂(apical) role (Cu–N 2.007(2), Cu–O(amide) 2.295(2) and 2.305(2) Å), thus showing a remarkable conformational flexibility.     

A novel uranyl complex UO2(tci)(C3H5N2) · H2O: Synthesis,crystal structure and characterization

Reaction of uranium oxynitrate hexahydrate with tris(2-carboxyethyl)isocyanurate (tciH₃) in acidic aqueous solution (pH ～4–5) yields the compound UO₂(tci)(C₃H₅N₂) · H₂O. X-ray diffraction shows that the uranyl ion is in a hexagonal bipyramid structure. Uranium ion in the complex is found to be ligated with three chelating COO^? groups at the equatorial plane, two oxygen atoms linking to uranium atom formed the vertical axis. The complex has the layered topology structure in the space. The thermal analysis verifies the component and the structure of the complex.