Syntheses and structural determination of the nine-coordinate rare earth metal complexes: [TbIII(Eg3a)(H2O)2] · 4.5H2O and K[TbIII(Edta)(H2O)3] · 5H2O

Two title complexes, [Tb^III(Eg3a)(H₂O)₂] · 4.5H₂O (I) (H₃Eg3a = 3-carboxymethyl-6, 9-dioxa-3,12-diazatetradecanedioic acid) and K[Tb^III(Edta)(H₂O)₃] · 5H₂O(II) (H₄Edta = ethylenediamine-N,N,N′,N′-tetraaceti acid), were prepared and characterized by FT-IR, elemental analyses, TGA-DTA-DTG, and single-crystal X-ray diffraction technique. For I, the Tb³⁺ ion is nine-coordinated by an Eg3a ligand and two coordination water molecules, yielding a monocapped square-antiprismatic (MCSAP) conformation. Complex I crystallizes in the monoclinic system with P2₁/c space group. The crystal data are as follows: a = 9.237(3), b = 10.018(3), c = 23.580(7) Å, β = 99.021(5)°, V = 2155.2(11) ų, Z = 4, ρ = 1.822 Mg m^?3, μ = 3.353 mm^?1, F(000) = 1180, R ₁ = 0.0445 and wR ₂ = 0.1034 for 4262 observed reflections with I ≥ 2σ(I). For II, the Tb³⁺ ion is nine-coordinated by an Edta ligand and three coordinate water molecules also yielding a MCSAP conformation. Complex II crystallizes in the orthorhombic system with Fdd2 space group. The crystal data are as follows: a = 19.373(5), b = 35.429(10), c = 12.114(3) Å, V = 8315(4) ų, Z = 16, ρ = 2.014 Mg m^?3, μ = 2.014 mm^?1, F(000) = 5024, R ₁ = 0.0224 and wR ₂ = 0.0557 for 3189 observed reflections with I ≥ 2σ(I). The potassium cations bridge the coordination spheres yielding many infinite long 1-D zigzag-type chains. The molecular structure of I is more stable than that of II. According to thermal analyses, the collapsing temperatures of crystal structure are 314°C for I and 348°C for II, which indicates that the crystal structure of II is more stable.     

K3[GdⅢ(nta)2(H2O)]·6H2O和(NH4)·[GdⅢ(Cydta)(H2O)2]·5H2O的合成及晶体结构

GdⅢ的配合物常被用作MRI造影剂[1,2]. GdⅢ的离子半径和电子结构分别为0.107 8 nm和高自旋f 7, 理论预测应与氨基多羧酸类配体形成稳定的九配位配合物[3～5]. 为证实理论预测并在此基础上寻找合适的可用于定向修饰的配体以及为提高GdⅢ配合物的脂溶性使其具有更好的细胞渗透性, 选择四齿配体nta和含有脂环烃的六齿配体Cydta分别合成了GdⅢ的配合物, 并测定了它们的分子结构. 结果显示, GdⅢ与nta形成九配位配合物, GdⅢ与Cydta形成八配位配合物.     

Syntheses and structural determinations of the nine-coordinate rare earth metal: Na4[DyIII(dtpa)(H2O)]2·16H2O,Na[DyIII(edta)(H2O)3]·3.25H2O and Na3[DyIII(nta)2(H2O)]·5.5H2O

Three complexes, Na₄[Dy^III(dtpa)(H₂O)]₂?·?16H₂O, Na[Dy^III(edta)(H₂O)₃]?·?3.25H₂O and Na₃[Dy^III (nta)₂(H₂O)]?·?5.5H₂O, have been synthesized in aqueous solution and characterized by FT–IR, elemental analyses, TG–DTA and single-crystal X-ray diffraction. Na₄[Dy^III(dtpa)(H₂O)]₂?·?16H₂O crystallizes in the monoclinic system with P2₁/n space group, a?=?18.158(10)?Å, b?=?14.968(9)?Å, c?=?20.769(12)?Å, β?=?108.552(9)°, V?=?5351(5)?ų, Z?=?4, M?=?1517.87?g?mol^?1, D _c?=?1.879?g?cm^?3, μ?=?2.914?mm^?1, F(000)?=?3032, and its structure is refined to R ₁(F)?=?0.0500 for 9384 observed reflections [I?>?2σ(I)]. Na[Dy^III(edta)(H₂O)₃]?·?3.25H₂O crystallizes in the orthorhombic system with Fdd2 space group, a?=?19.338(7)?Å, b?=?35.378(13)?Å, c?=?12.137(5)?Å, β?=?90°, V?=?8303(5)?ų, Z?=?16, M?=?586.31?g?mol^?1, D _c?=?1.876?g?cm^?3, μ?=?3.690?mm^?1, F(000)?=?4632, and its structure is refined to R ₁(F)?=?0.0307 for 4027 observed reflections [I?>?2σ(I)]. Na₃[Dy^III(nta)₂(H₂O)]?·?5.5H₂O crystallizes in the orthorhombic system with Pccn space group, a?=?15.964(12)?Å, b?=?19.665(15)?Å, c?=?14.552(11)?Å, β?=?90°, V?=?4568(6)?ų, Z?=?8, M?=?724.81?g?mol^?1, D _c?=?2.102?g?cm^?3, μ?=?3.422?mm^?1, F(000)?=?2848, and its structure is refined to R ₁(F)?=?0.0449 for 4033 observed reflections [I?>?2?σ(I)]. The coordination polyhedra are tricapped trigonal prism for Na₄[Dy^III(dtpa)(H₂O)]₂?·?16H₂O and Na₃[Dy^III(nta)₂(H₂O)]?·?5.5H₂O, but monocapped square antiprism for Na[Dy^III(edta)(H₂O)₃]?·?3.25H₂O. The crystal structures of these three complexes are completely different from one another. The three-dimensional geometries of three polymers are 3-D layer-shaped structure for Na₄[Dy^III(dtpa)(H₂O)]₂?·?16H₂O, 1-D zigzag type structure for Na[Dy^III(edta)(H₂O)₃]?·?3.25H₂O and a 2-D parallelogram for Na₃[Dy^III(nta)₂(H₂O)]?·?5.5H₂O. According to thermal analyses, the collapsing temperatures are 356°C for Na₄[Dy^III(dtpa)(H₂O)]₂?·?16H₂O, 371°C for Na[Dy^III(edta)(H₂O)₃]?·?3.25H₂O and 387°C for Na₃[Dy^III(nta)₂(H₂O)]?·?5.5H₂O, which indicates that their crystal structures are very stable.     

A coordination polymer with a (3,4)-connected (4·62)2(42 ·62 ·82) 2D network: synthesis,crystal structure and luminescent properties

The 2D Zn(II) coordination polymer with 2,3-dicarboxypyridine acid (2,3-H₂PDC) and dimethylamine (DMA) [Zn(2,3-PDC)(DMA)] _n (1) was synthesized under solvothermal conditions and characterized by FT-IR spectroscopy, TGA and luminescent analysis. X-ray crystallographic studies of 1 reveal that this metal-organic complex has an interesting (3,4)-connected 2D network with binary nodes. The Zn ions are four-connected nodes and the 2,3-PDC ligands are three-connected nodes. Luminescent study indicates 1 has an emissive maximum at 403?nm in the solid state at room temperature.     

[Gd(Gly)3(H2O)2]Cl3·H2O的合成与晶体结构

氯化钆;甘氨酸;固态配合物;[Gd(Gly)3(H2O)2]Cl3·H2O的合成与晶体结构     

Hydrothermal Synthesis, Crystal Structure and Thermal Stability of [Ni(phen)3]·(C8H12O4)·(H2O)14

One novel complex [Ni(phen)3]·(C8H12O4)·(H2O)14 with hexane dicarboxylic acid and 1,10-phenanthroline has been hydrothermally synthesized and characterized. Crystal data: monoclinic, space group C2/c, a = 2.3475(5), b = 1.2208(2), c = 1.9499(4) nm, β = 114.682(3)o, V = 5.0778(16) nm3, Dc = 1.339 g/cm3, Z = 4, μ(MoKα) = 0.458 mm-1, F(000) = 2168, GOOF = 1.014, R = 0.0401 and wR = 0.0961. The nickel(Ⅱ) center in the title complex is coordinated with six nitrogen atoms of three 1,10-phenanthroline molecules, giving a distorted octahedral coordination geometry. However, the nickel(Ⅱ) ion does not coordinate to the hexane dicarboxylic acid. The complex molecules form a 3D structure through hydrogen bonds. TG analysis shows that the title complex is stable below 240.0 ℃.     

Keggin polyoxoanion supported organic-inorganic trinuclear lutetium cluster, {Na(H(2)O)(3)[Lu(pydc)(H(2)O)(3)](3)}[SiW(12)O(40)]·26.5H(2)O

A novel strawberry-like organic-inorganic hybrid, {Na(H(2)O)(3)[Lu(pydc)(H(2)O)(3)](3)}[SiW(12)O(40)]·26.5H(2)O (H(2)pydc = pyridine-2,6-dicarboxylate) containing an intriguing trinuclear lutetium cluster {Na(H(2)O)(3)[Lu(pydc)(H(2)O)(3)](3)}(4+) has been synthesized and its luminescent properties, IR, UV, TG, PXRD analyses and single crystal X-ray diffraction were investigated.     

Synthesis,crystal structure and properties of a novel 1D chain organic–inorganic rare earth coordination polymer: Gd0.5H0.5{[Gd(H2O)6] [Gd(H2O)2(DMSO)] [α-SiW11O39]}·7H2O

A 1D chain organic–inorganic rare earth coordination polymer Gd_0.5H_0.5{[Gd(H₂O)₆] [Gd(H₂O)₂(DMSO)][α-SiW₁₁O₃₉]}·7H₂O has been synthesized by reaction of α-K₈SiW₁₁O₃₉·13H₂O, HClO₄, Gd₂O₃ with dimethyl sulfoxide (DMSO) and characterized by elemental analysis, IR, UV, ESR spectra and X-ray diffraction. The title compound crystallizes in a monoclinic lattice, P2₁/c space group, with a?=?23.544(5), b?=?11.527(2), c?=?23.297(5)?Å, β?=?109.05(3)°, V?=?35976(2)?ų, Z?=?4, R ₁?=?0.0838, wR ₂?=?0.1300. The neighboring polyanion units {[Gd(H₂O)₆][Gd(H₂O)₂(DMSO)][α-SiW₁₁O₃₉]}^2? are bridged together forming a 1D chain structure by means of [Gd(H₂O)₂(DMSO)]³⁺ ions. The ESR spectra of the title compound at room temperature are composed of eight lines, indicating the strong effect of the crystal field generated by the nearest surrounding ligands of the Gd^III cation.     

Hydrothermal Synthesis and Structure of a Novel Coordination Polymer Co3(tma)(pda)2(H2O)3]n·nH2O

A novel coordination polymer [Co3(tma)(pda)2(H2O)3]n·nH2O was synthesized by hydrothermal reaction of 3-(3-pyridyl)acrylate acid (pda) and trimesic acid (tma) with CoCl2·6H2O. The structure was characterized by elemental analysis, IR spectroscopy and X-ray single-crystal dif- fraction analysis. It crystallizes in triclinic, space group (P1)with a = 9.569(4), b = 12.562(6), c = 12.666(6)(A), α = 97.321(7), β = 110.295(7), γ = 106.110(7)°, V = 1328.9(10)(A)3, Dc = 1.877 g/cm3, Mr = 751.24, Z = 2, μ = 1.930 mm-1, F(000) = 758, the final R = 0.0392 and wR = 0.0837. The diffraction result shows that Co atoms are linked through pda and tma ligands to form an infinite three-dimensional network.     

新型无机-有机杂化微孔晶体Cd3(BDC)0.5(BTC)2(DMF)(H2O)·3DMF·H3O·H2O的合成与结构

传统分子筛是以硅氧四面体和铝氧四面体为骨架的微孔晶体材料. 近年来, 以无机-有机结构单元为骨架组成的微孔晶体材料已引起人们的广泛关注[1～19]. 该类材料是由金属离子(或金属氧簇)与有机配体(大多数是芳香多酸和多碱)构成的建筑单元通过共价键或者分子间作用力构成的. 无机-有机杂化晶体材料有多种结构类型, 如1-D, 2-D, 3-D和笼状结构等.     

Cs8U(IV)(U(VI)O2)3(Ge3O9)3·3H2O: a mixed-valence uranium germanate with 9-ring channels

A mixed-valence uranium(IV,VI) germanate has been synthesized under high-temperature, high-pressure hydrothermal conditions. The structure contains discrete U(IV)O(6) octahedra and U(VI)O(6) tetragonal bipyramids, which are connected by three-membered single-ring Ge(3)O(9)(6-) anions to form a three-dimensional framework with 9-ring channels. The U 4f X-ray photoelectron spectroscopy spectrum was measured to identify the valence states of the uranium.     

A new phase in the MnII–SeIV–MoVI–O system,Mn(MoO3)(SeO3)(H2O): Hydrothermal synthesis,crystal structure and properties

A new phase in the Mn^II–Se^IV–Mo^VI–O system, Mn(MoO₃)(SeO₃)(H₂O) (1), has been hydrothermally synthesized with a high yield (82%), and characterized by IR, TG-DSC, magnetism measurement and single crystal X-ray diffraction. The structure of Mn(MoO₃)(SeO₃)(H₂O) features a complicated 3D network composed of the 1D molybdenum(VI) oxide chains and the 1D manganese(II) selenite chains interconnected via Se–O–Mo and Mn–O–Mo bridges. It is stable up to approximately 340 °C, and losses water molecule at 340 °C, then release SeO₂ at about 420 °C. The result of magnetic property measurements has indicated that there exist antiferromagnetic interactions between Mn(II) centers. Photocatalysis experimental result illustrates that the compound exhibits good photocatalytic performance for degradation of RhB under visible light irradiation.     

Synthesis and Crystal Structure of Mn(phen)(CF3COO)(H2O)3·NO3

The mononuclear manganese complex Mn(phen)(CF3COO)(H2O)3(NO3 (C14H14O8N3F3Mn) has been synthesized, where phen = 1,10-phenanthroline. The molecular and crystal structures were determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/c with a = 8.8550(3), b = 10.6529(3), c = 19.8763(2) A, β = 97.762(2)o, V = 1857.78(8) A3, Z = 4, Mr = 464.22, Dc = 1.660 g/cm3, μ = 0.789 mm-1, F(000) = 940, T = 293(2) K, R = 0.0764 and wR = 0.2441 for 1995 observed reflections with I > 2σ(I). In the crystal the manganese atom is six-coordinated by two chelated nitrogen atoms from phenanthroline, three oxygen atoms from water molecules and one oxygen atom from trifluoroacetate, completing an octahedral geometry.     

A Pseudo-Keggin Compound:Hydrothermal Synthesis and Crystal Structure of (DETAH)(DETAH3)3[V18O42(PO4)]·(PO4)·2H2O

The novel vanadophosphate (DETAH)(DETAH3)3[V18O42(PO4)]·(PO4)·2H2O has been synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic, space group C2/c with a=23.857(3), b=12.9619(18), c=20.204(3) (A), β=105.692(2)°, V=6015.0(14) (A)3, Z=4, Dc=2.473 g/cm3, Mr=2239.68, F(000)=4432, R=0.0725, wR=0.1524 and GOOF=1.095. The metaloxo cluster contains a novel six-capped pesudo-Keggin structure unit which encloses a disorder PO43- guest.     

Syntheses and Crystal Structures of (H3O)(C3H5N2)[Mn(OH)6 Mo6O18]·3.5H2O and (H3O)3[Co(OH)6Mo6O18]·7H2O

The crystals of the title compounds (H3O)(C3H5N2)[Mn(OH)6Mo6O18]·3.5H2O 1 and (H3O)3[Co(OH)6Mo6O18]·7H2O 2 have been prepared and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 21.5018(9), b = 10.9331(5), c = 11.8667(5)A,β = 95.3570(10)o, V = 2777.5(2)A3, Z = 4, Dc = 2.802 g/cm3, Mr = 1171.80,μ(MoKα) = 3.173 mm-1, F(000) = 223, the final R = 0.0458 and wR = 0.1041 for 2093 observed reflections (I>2σ(I)); Compound 2 crystallizes in monoclinic, space group P21/c with a = 11.4042(12), b = 10.9481(11), c = 11.6722(12)A, β= 99.948(2)o, V = 1435.4(3)A3, Z = 2, Dc = 2.794 g/cm3, Mr = 1207.80,μ(MoKα) = 3.223 mm-1, F(000) = 1160, the final R = 0.0544 and wR = 0.1066 for 1906 observed reflections (I > 2σ(I)). Both compounds 1 and 2 adopt the Anderson structure, in which the anion is of centrosymmetry and formed by six octahedral edge-sharing MoO6 units surrounding the central MO6 (M = Mn or Co) octahedron.     

Synthesis and Structural Characterization of Gd(Ⅱ) Coordination Polymer [Gd2(μ-phth)3(b-pd)(H2O)5]n

A new Gd(Ⅱ) complex [Gd2(μ-phth)3(b-pd)(H2O)5]n (phth = o-phthalato, b-pd = N,N- bipyridine) has been synthesized by the reaction of GdO2 with o-phthalate, H2O and 2,2′-bipyridine. The crystal structure has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P with a = 11.82920(10), b = 13.53550(10), c = 13.7381(2)(A), α = 88.99, β = 66.9120(10), γ = 66.2370(10)°, V = 1826.02(3)(A)3, Dc = 1.915 g/cm3, C34H30N2O17Gd2, Mr = 1053.10, F(000) = 1024, μ = 3.680 mm-1, Z = 2, R = 0.0612 and wR = 0.1320 for 6259 observed reflections (I > 2σ(I)). In the title complex, the Gd(II) ions are bridged by o-phthalate ligands in a bidentate mode, producing a 1D infi- nite chain structure. Each eight-coordinated Gd(Ⅱ) center is coordinated by eight oxygen atoms from phth to give a distorted dodecahedral geometry, and each nine-coordinated Gd(Ⅱ) center is coordi- nated by two N atoms from b-pd and seven oxygen atoms from phth to give a distorted geometry of capped square antiprism. The chains are linked by π-π interactions and hydrogen bonds between oxy- gen atoms of carboxylate groups and H2O molecules and hydrogen atoms of H2O, b-pd and o-phth molecules, forming an unusual three-dimensional coordination polymer.     

A new cation induced chain-like complex [Cu(H2tea)(H2O)(imi)][Cu(H3tea)(imi)][Na{Mo8O26}] · 4H2O

A new complex [Cu(H₂tea)(H₂O)(imi)][Cu(H₃tea)(imi)][Na{Mo₈O₂₆}] · 4H₂O (H₃tea =triethanolamine, imi = imidazole) has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. X-ray diffraction reveals that β-[Mo₈O₂₆]^4? polyanions are linked by sodium ions to form a chain. The coppers are five- and six-coordinate for [Cu(H₃tea)(imi)]²⁺ and [Cu(H₂O)(H₂tea)(imi)]⁺, respectively. Crystal packing is due to hydrogen bonds and π ··· π stacking interactions, giving a 3-D polymeric network. The magnetic properties of the title compound are also presented.     

[Ni(bpy)(mal)(H2O)3]·H2O and [Ni(4,4′-dmbpy)(mal)(H2O)3]·1.5H2O: syntheses,crystal structures,magnetic properties,and computational study of stacking interactions

[Ni(bpy)(mal)(H₂O)₃]·H₂O and [Ni(4,4′-dmbpy)(mal)(H₂O)₃]·1.5H₂O (mal = maleato; bpy = 2,2′-bipyridine; 4,4′-dmbpy = 4,4′-dimethyl-2,2′-bipyridine) exhibit molecular crystal structures. The Ni(II) central ions in both complexes are six-coordinate by one chelate bonded L–L ligand, three aqua ligands, and one position is occupied by a maleato oxygen donor atom. Hydrogen bonded ribbon-like supramolecular structural motifs are present in both studied complexes; these are linked by weaker C–H?O hydrogen bonds in [Ni(bpy)(mal)(H₂O)₃]·H₂O, whereas in [Ni(4,4′-dmbpy)(mal)(H₂O)₃]·1,5H₂O the hydrogen bonded ribbons are linked by O?H-O-H?O hydrogen bonds with the participation of the additional water solvate molecule positioned on the twofold axis. In both structures, π–π stacking interactions with different patterns in respective structures were found. The role of dispersion energy and many-body effects in the stabilization of bpy and 4,4′-dmbpy stacking interactions were investigated using methods of computational chemistry. Those confirm the dispersion-dominated stabilization of the 4,4′-dmbpy supramolecular chain-like structure, with only marginal impact of cooperativity effects. Thermal decompositions of both complexes start with dehydration. Magnetic susceptibility studies performed from 2 to 300 K revealed a dominant effect of the zero-field splitting of the Ni(II) ion, governing the low-temperature magnetic properties of both compounds.