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1.
The reaction of an ethanolic solution 2,6‐pyridinedicarboxylic acid ( 1 , LH2) with TlNO3 in the presence of triethylamine led to the coordination polymer [Tl(LH)]n ( 2 ). The complex was characterized by elemental analysis, IR spectroscopy and single‐crystal X‐ray diffraction. Crystal data for 2 at –80 °C: monoclinic, space group I2/a, a = 696.1(1), b = 1190.6(2), c = 931.0(2) pm, β = 103.28(1)°, Z = 4, R1 = 0.0256.  相似文献   

2.
The reaction of solution 2,6‐pyridinedicarboxylic acid ( 1 ) and 2,2′‐Bipyridine with Pb(NO3)2 led to the coordination polymer [Pb(pydc)]n ( 2 ) (pydcH2 is 2,6‐pyridinedicarboxylic acid). This complex was characterized by elemental analysis, IR spectroscopy and single‐crystal structure of 2 . Crystal data for 2 at ?80 °C: monoclinic, space group P21/n, a = 977.2(1), b = 554.0(1), c = 1425.3(2) pm, β = 104.75(1)°, Z = 4, R1= 0.0261. The units [Pb(pydc)] form infinite chains along [010].  相似文献   

3.
The novel 1,10‐phenanthroline‐2,9‐dicarboxylate containing Chromium(III) complex, (pydaH)[Cr(phendc)2] · 5H2O, was synthesized using proton‐transfer compound LH2, (pydaH2)2+(phendc)2?, (pyda: 2,6‐pyridinediamine; phendcH2: 1,10‐phenanthroline‐2,9‐dicarboxylic acid) and thoroughly characterized by elemental analysis, IR spectroscopy, X‐ray crystallography and cyclic voltammetry. The complex crystallizes in the monoclinic space group P21/n with four formula units in the unit cell. The unit cell dimensions are: a = 13.962(3) Å, b = 14.529(3) Å, c = 16.381(3) Å and β = 106.691(4)°. In this complex, 1,10‐phenanthroline‐2,9‐dicarboxylate acts as a tridentate ligand and the lattice is composed of anionic hexacoordinated complex, [Cr(phendc)2]?, 2,6‐pyridiniumdiamine counter ion, (pydaH)+, and five lattice water molecules. Crystallographic characterization revealed that the resulting supramolecular structure is strongly stabilized by complicated network of hydrogen bonds between the crystallization water molecules, counter ion and both coordinated and uncoordinated carboxylate groups. There is no relevant π‐π interaction for this anionic complex between pyda or phendc moieties. The electrochemical studies indicated over potential for both the cathodic and anodic peaks of the complex with respect to the free Cr3+ ion, as a consequence of the energy requirement for rearrangement of the ligand at electrode surface.  相似文献   

4.
The reaction of 2,6‐pyridinedicarboxylic acid ( 1 , LH2) with CeCl3·7H2O and Sm(NO3)3·6H2O in the presence of triethylamine led to the coordination polymer complexes [M(L)(LH)(H2O)2]·4H2O [M = Ce ( 2 ) and Sm ( 3 )]. Both complexes were characterized by elemental analyses, IR spectroscopy and the crystal structures of 2 and 3 . Crystal data for 2 at ?80 °C: monoclinic, space group P21/c, a = 1404.6(1), b = 1122.1(1), c = 1296.1(1) pm, β = 102.09(1)°, Z = 4, R1 = 0.0217 and for 3 at ?80 °C: monoclinic, space group P21/c, a = 1395.1(1), b = 1120.1(1), c = 1282.8(1) pm, β = 102.71(1)°, Z = 4, R1 = 0.019.  相似文献   

5.
合成了3,4-二甲氧基苯乙酸邻菲啰啉镱(III)配合物(C84H82Yb2N4O24): [Yb2(DMPA)6(phen)2](HDMPA=3,4-二甲氧基苯乙酸(C12H12O4), phen=1,10-邻菲啰啉)(CCDC: 757541), 并通过元素分析、红外(IR)光谱、热重分析(TG-DTG)对其进行了表征, 用单晶X射线衍射测定了配合物的晶体结构. 配合物C84H82Yb2N4O24属三斜晶系, 空间群P1, 晶胞参数: a = 1.22877(14) nm, b=1.23235(16) nm, c=1.45234(19) nm, α=91.726(7)°, β=103.321(7)°, γ=113.885(6)°, 晶胞体积: V=1.9379(4) nm3, 晶胞内分子数Z=1, 相对分子质量Mr=1877.62, 电子数F(000)=946, 密度Dc=1.609 g·cm-3, 吸收系数μ(Mo Kα)=2.481 mm-1. 测定了铕和铽掺杂(2.5%, 5.0%, 10.0%, 摩尔分数)的配合物的荧光光谱, 结果表明, 单独的配体没有荧光, 在形成配合物后, 依然显示铕(III)离子和铽(III)离子的特征发射峰, 这表明配体将吸收的能量有效地转移给了中心离子, 配体起到了很好的敏化作用.  相似文献   

6.
Three ternary rare earth [NdIII ( 1 ), SmIII ( 2 ) and YIII ( 3 )] complexes based on 3‐[(4,6‐dimethyl‐2‐pyrimidinyl)thio]‐propanoic acid (HL) and 1,10‐phenanthroline (Phen) were synthesized and characterized by IR and UV/Vis spectroscopy, TGA, and single‐crystal X‐ray diffraction. The crystal structures showed that complexes 1 – 3 contain dinuclear rare earth units bridged by four propionate groups and are of general formula [REL3(Phen)]2 · nH2O (for 1 and 2 : n = 2; for 3 : n = 0). All rare earth ions are nine‐coordinate with distorted mono‐capped square antiprismatic coordination polyhedra. Complex 1 crystallizes in the monoclinic system, space group P21/c with a = 16.241(7) Å, b = 16.095(7) Å, c = 19.169(6) Å, β = 121.48(2)°. Complex 2 crystallizes in the monoclinic system, space group P21/c with a = 16.187(5) Å, b = 16.045(4) Å, c = 19.001(4) Å, β = 120.956(18)°. Complex 3 crystallizes in the triclinic system, space group P1 with a = 11.390(6) Å, b = 13.636(6) Å, c = 15.958(7) Å, α = 72.310(17)°, β = 77.548(15)°, γ = 78.288(16)°. The antioxidant activity test shows that all complexes own higher antioxidant activity than free ligands.  相似文献   

7.
Three new complexes of group thirteen metals, gallium(III), indium(III), and thallium(III) with proton transfer compounds, obtained from 2,6‐pyridinedicarboxylic acid (dipicolinic acid), were synthesized and characterized using elemental analysis, IR, 1H and 13C NMR spectroscopy and single crystal X‐ray diffraction. The gallium(III) and indium(III) complexes were prepared using (pydaH2)(pydc) (pyda = 2,6‐pyridinediamine, pydcH2 = dipicolinic acid) and thallium(III) complex was obtained from (creatH)(pydcH) (creat = creatinine). The chemical formulae and space groups of the complexes are (pydaH)[Ga(pydc)2] · 3.25H2O · CH3OH, ( 1 ), [In(pydc)(pydcH)(H2O)2] · 5H2O, Pna21 ( 2 ) and [Tl2(pydcH)3(pydc)(H2O)2], ( 3 ). Non‐covalent interactions such as ion‐pairing, hydrogen bonding and π‐π stacking are discussed. The complexation reactions of pyda, pydc, and pyda + pydc with In3+ and Ga3+ ions in aqueous solution were investigated by potentiometric pH titrations, and the equilibrium constants for all major complexes formed are described.  相似文献   

8.
A novel proton transfer compound, (GH)2(phendc), ( 1 ), was synthesized from the reaction of 1,10‐phenanthroline‐2,9‐dicarboxylic acid, phendcH2, and guanidine hydrochloride, (GH)(Cl), (G: guanidine). The characterization was performed using IR, 1H and 13C NMR spectroscopy. The cobalt(II) compounds were synthesized using proton transfer compounds containing guanidinium counter ion. These proton transfer compounds are (GH)2(phendc), and (GH)2(pydc) (pydcH2: 2,6‐pyridinedicarboxylic acid). The chemical formulae and space groups are (GH)2[Co(phendc)2]·4H2O, (2) , and (GH)2[Co(H2O)6][Co(pydc)2]2, P21/n (3) . Non‐covalent interactions such as ionpairing, hydrogen bonding and π‐π stacking are discussed.  相似文献   

9.
The proton transfer compound LH2 , (phenH+)2(pydc2—), has been prepared from 1, 10‐phenanthroline, phen, and 2, 6‐pyridinedicarboxylic acid, (dipicolinic acid), pydcH2. Characterization was performed using solution and solid phase CP/MAS 13C NMR and IR spectroscopy. The reactions of this adduct with ZnSO4·7H2O and Zn(NO3)2·4H2O give the complexes, [Zn(pydc)2][Zn(phen)2(H2O)2]·7H2O (1) and [Zn(phen)3]4(H(Hpydc)2)(NO3)7·26H2O (2) , respectively. These complexes were characterized by 1H and 13C NMR spectroscopy and single crystal X‐ray analysis. The complexes crystallize in the triclinic space group P1 with Z = 2. The unit cell dimensions for complex 1 and 2 are: a = 9.9838(9) Å, b = 14.7483(13) Å, c = 14.8365(13) Å and a = 12.640(4) Å, b = 15.855(5) Å, c = 21.830(7) Å, respectively. In complex 1 (pydc2—) and phen, are tri‐ and bidentate ligands, respectively, and an anionic [Zn(pydc)2]2— and cationic [Zn(phen)2(H2O)2]2+ complex are formed simultaneously. In complex 2 , three phen participate in complexation leaving hydrogen‐bis(pyridine‐2‐carboxylate), (H(Hpydc)2) as a supramolecular anion. The fragments (H(Hpydc)2), 7 NO3, and 26 H2O in complex 2 are joined together by extensive and strong H‐bonding; therefore, the structure is composed of [Zn(phen)3]48+, and an anionic hydrogen bond supramolecular assembly with the formula, {(H(Hpydc)2(NO3)7)8— · 26H2O}n. The anionic species (H(Hpydc)2) has a special position at the inversion center, as well as one of the NO3 anions, which is disordered over the inversion center. Most of the hydrogen bonds in complex 2 represent strong H‐bonding. The protonation constants of the building blocks of the pydc‐phen adduct, the equilibrium constants for the reaction of (pydc2—) with phenanthroline and the stoichiometry and stability of the ZnII complex with LH2 on aqueous solution were determined by potentiometric pH titration. The solution study results support self‐association between (pydc2—) and (phenH+) with a stoichiometry for the Zn(II) complex similar to that observed for the isolated crystalline complex.  相似文献   

10.

The complex [Cu(l-Leu)(phen)(H2O)]NO3 has been synthesized and characterized by elemental analysis, molar conductivity, spectroscopic and X-ray diffraction methods, where phen = 1,10-phenanthroline and l-Leu = l-leucinate. The complex crystallizes in the triclinic space group Pī with two molecules in a unit cell of dimensions a = 7.288(4) Å, b = 11.588(7) Å, c = 12.349(3) Å, α = 86.388(10)o, β = 76.175(11)°, γ = 72.132(3)°, V = 963.8(10) Å3, Z = 2, D c = 1.564 g/cm3, μ = 1.177 mm?1, F(000) = 470, R 1 = 0.0611, and wR 2 = 0.0711. The copper(II) is ligated in a distorted square-pyramidal geometry by the two nitrogen atoms of phen and the amino nitrogen atom and one carboxylate oxygen atom from each independent l-Leu moiety in the basal plane, and one water oxygen at the apical position. A supramolecular configuration is formed from strong phen-phen stacking interactions between neighboring [Cu(l-leu)(phen)(H2O)]+cations in the crystal.  相似文献   

11.
The two complexes (pydaH)2[Ce(pydc)2(H2O)2]2 · 2H2O (1) and (phenH)2[Bi(pydc)2(H2O)]2 · 5H2O (2) were prepared from the proton transfer compounds containing the 2,6‐pyridinedicarboxylate ion. 1 was synthesized from the reaction of Ce(NO)3 · 6H2O with the proton transfer compound, (pydaH2)(pydc), (pyda=2,6‐diaminopyridine, pydcH2=2,6‐pyridinedicarboxylic acid). 2 was synthesized from the reaction of proton transfer compound, (phenH)2(pydc), (phen=1,10‐phenanthroline), with Bi(NO3)3 · 5H2O. The characterization was carried out using IR, 1H and 13C NMR spectroscopy, elemental analysis and single crystal X‐ray diffraction. The complex 1 crystallizes in the space group of the triclinic system, and contains two molecules per unit cell. The structure has been refined to a final value for the crystallographic R factor of 0.0342 based on 8851 reflections. The unit cell parameters are: a = 9.753(2) Å, b = 10.503(2) Å, c = 10.774(2) Å, α = 83.905(4)°, β = 88.089(4)°, and γ = 82.636(3)°. The crystal structure illustrates that cerium atoms are connected together through the four‐membered ring Ce2O2. 2,6‐Pyridinedicarboxylate fragment acts as a tridentate ligand. The molecular structure contains four (pydc)2? ligands, two of which are bridge ligands linking the two central atoms. The complex 2 crystallizes in the space group of the triclinic system and contains two molecules per unit cell. The unit cell dimensions are: a = 8.8860(4) Å, b = 12.0132(6) Å, c = 13.0766(6) Å, α = 100.967(1)°, β = 96.681(1)° and γ = 94.191(1)°. The structure has been refined to a final value for the crystallographic R factor of 0.0471 based on 9576 reflections. In this complex, 2,6‐pyridinedicarboxylate moiety has acted as a tridentate ligand and the lattice is composed of binuclear unit, [Bi(pydc)2(H2O)]22?, (phenH)+ counter ions and five lattice waters. In both complexes hydrogen bonds, π‐π stacking and ion‐pairing play important roles in stabilizing the corresponding lattice. The stoichiometry and stability of the ZnII, CdII, PbII, and CeIII complexes with (pydaH2)(pydc) in aqueous solution were investigated by potentiometric pH titration. The solution studies revealed that the stoichiometry of the crystalline complexes of the proton transfer system (pydaH2)(pydc) with CeIII, obtained in this study, and those with ZnII, CdII and PbII, reported in our previous studies, are in close agreements. The complexation reactions of phen, pydc, and 2phen+pydc with BiIII in aqueous solution were investigated by potentiometric pH titrations, and the equilibrium constants for all major complexes formed are described.  相似文献   

12.
A binuclear samarium(III) complex with benzoic acid and 1,10‐phenanthroline, [Sm(BA)3phen]2 was synthesized and characterized by elemental analysis, UV, IR and TG‐DTG techniques. The structure of the title complex was established by single crystal X‐ray diffraction. The crystal is triclinic, space group P1 with a = 10.8216(11) Å, b = 11.9129(13) Å, c = 12.425(2) Å, α = 105.007(2)°, β = 93.652(2)°, γ = 113.2630(10)°, Z = 1, Dc = 1.650 mg·m?3, F(000) = 690. The carboxylate groups are bonded to the samarium ion in three modes: bidentate chelating, bidentate bridging, and tridentate chelating‐bridging. Each Sm3+ ion is coordinated to one bidentate chelating carboxylate group, two bidentate bridging and two tridentate chelating‐bridging carboxylate groups, as well as one 1,10‐phenanthroline molecule, forming a nine‐coordinate metal ion. Based on thermal analysis, the thermal decomposition process of [Sm(BA)3phen]2 has been derived.  相似文献   

13.
The 1:1 proton transfer compound LH2, (creatH)+ (pydcH)?, has been prepared from the reaction of creatinine, creat, and dipicolinic acid, pydcH2, (2, 6‐ pyridinedicarboxylic acid) and characterized using IR, 1H and 13C NMR spectroscopy. The first coordination complex (creatH)[Zn(pydc)(pydcH)]·4H2O, was prepared using LH2 and zinc(II) nitrate, and characterized using IR, 1H and 13C NMR spectroscopy and single crystal X‐ray crystallography. The crystal system is triclinic with space group with two molecules per unit cell. The unit cell dimensions are a = 8.085(2) Å, b = 10.802(4) Å, c = 13.632(4) Å, α = 104.98(2)°, β = 90.31(2)° and γ = 92.55(3)°. The structure has been refined to a final value for the crystallographic R factor of 0.0381 based on 3003 reflections. The zinc atom is six‐coordinated with a distorted octahedral geometry. The (pydc)2? and (pydcH)? units are almost perpendicular to each other. Extensive hydrogen bondings between carboxylate groups, (creatH)+ and water molecules throughout the zinc(II) complex as well as π–π stacking and ion pairing play important roles in stabilizing the corresponding lattices. The protonation constants of the building blocks of the pydcH2‐creat adduct, the equilibrium constants for the reaction of (pydc)2? with creat and the stoichiometry and stability of the ZnII complex with LH2 in aqueous solution were accomplished by potentiometric pH titration. The solution studies support a self‐associated (creatH)+(pydcH)? as the most abundant species at pH = 3.4. The stoichiometry of the crystalline complex (i.e. (creatH) [Zn(pydc)(pydcH)])and that of the most abundant species detected in solution were found the same.  相似文献   

14.
于杰辉  施展等 《中国化学》2002,20(6):560-563
The title compound Cu2Cl2phen (phen = 1,10‐phenanthroline, C12H8N2) 1 was synthesized from CuCl2·2H2O, CuCl and phen by hydrothermal method and its structure was determined by single crystal X‐ray analysis. With phen, CuG forms one‐dimensional chains, which comprise two zigzag chains based on fused Cu‐X units and connected via covalent bonds. The compound contains two crystallographically unique monovalent copper ions, Cu(1) and Cu(2). The Cu(1) atom in the tetrahedral site, is coordinated to two bridging Cl? and two N atoms in phen. The Cu(2) atom with a slightly distorted triangular planar geometry, is coordinated to three Cl?. The compound 1 was crystallized in monoclinic, space group P21/n with a = 0.37338(4), b = 1.9510(2), c = 1.68008(19) nm, β = 95.605 (3)°, R = 0.0458, and was characterized by elemental analysis, IR spectrum and TGA analysis.  相似文献   

15.
Iso‐type [MII(pdc)(DPphen)(H2O]·H2O compounds (M = Co or Cu, pdc = 2,6‐pyridinedicarboxylato(2‐) ligand and DPphen = 4,7‐diphenyl‐1,10‐Phenanthroline) were synthesized and studied by X‐ray diffraction, thermal and spectral methods. The N,N′‐equatorial bidentate DPphen‐copper(II) chelation imposes a mer‐N(equatorial)+O2(apical) conformation to pdc in the coordination polyhedron (type 4+1+1). In the Co(II) derivative, the coordination is of type 1+2+2+1 because of a lesser Jahn‐Teller distortion. In the crystals, π,π‐interligand interactions between phen ligands connect the complex molecules in multi‐stacked chains. Aqua···O(carboxyl) H‐bonding interactions reinforce the stacked chains and build double chains in 1D supramolecular structures parallel to the a axis. Non coordinated water connect these structures by H‐bonds.  相似文献   

16.
Two rare metal coordination complexes of yttrium(III) including 1,10‐phenanthroline, Y(phen)2(NO3)3 and (phenH)2[Y2(pydc)3(NO3)2·6H2O] (phen=1,10‐phenanthroline, pydc=2,6‐pyridinedicarboxylate), and a proton transfer compound (phenH+)2(pydc2?) were synthesized and characterized by elemental analysis, molar conductance, infrared spectra (IR), nuclear magnetic resonance (NMR) and thermal analysis. The proposed structures of yttrium complexes were exhibited. The in vitro biological activities of the newly synthesized complexes have also been investigated against Bacillus coli, Staphylococcus aureus and Candida albicans. The results showed that yttrium(III) complexes including 1,10‐phenanthroline exhibited better antibacterial/antifungal activity than their ligands and corresponding compounds.  相似文献   

17.
The syntheses and crystal structures of eight lanthanide complexes with formula [Ln(2,5‐DCB)x(phen)y] are reported, which are characterized via single‐crystal, powder X‐ray diffraction, elemental analysis, IR spectroscopy, thermogravimetric analysis, photoluminescence measurement, and DC/AC magnetic measurement. These eight complexes are isostructural, and possess a discrete dinuclear structure. The adjacent dinuclear molecules are linked by the hydrogen bonding interactions into a one‐dimensional (1D) supramolecular chain. The neighboring 1D chains are further extended into a two‐dimensional (2D) supramolecular layer by the π–π stacking interactions. The photoluminescent properties of complexes 1 (NdIII), 2 (SmIII), 3 (EuIII), 5 (TbIII), 6 (DyIII), and 8 (YbIII) were investigated. Magnetic investigations also reveal the presence of ferromagnetic interactions in complexes 4 (GdIII), 6 (DyIII), and 7 (ErIII). Additionally, complex 6 (DyIII) demonstrates field‐induced slow magnetic relaxation behavior.  相似文献   

18.
The syntheses, characterizations and in vitro cytotoxities of seven soluble silver (I) compounds (1–7) with 2,2′‐bipyridine (bpy), 5,5′‐dimethyl‐2,2′‐bipyridine (dmbpy) and 1, 10‐phenanthroline (phen) are described. Two of the complexes, [Ag(dmbpy)(NO3)] (1) and [Ag(dmbpy)]ClO4(2), have been structurally established by single‐crystal X‐ray diffraction, which reveals the silver(I) atom in compound 1 is in a Y‐shape coordination geometry with two N atoms (av. Ag? N = 227.8 pm) from a chelate dmbpy ligand and an O atom (Ag? O=221.8(4) pm) from a monodentate nitrate. The Ag(I) atom in compound 2 is three‐coordinated by three N atoms, two of which are from a chelate dmbpy, and one from an acetonitrile ligand. The seven compounds showed strong cytotoxities in vitro to both normal and carcinoma cells.  相似文献   

19.
20.
A novel seven‐coordinate dimer bis[(2,6‐pyridinedicarboxylato)(methanol)dibenzyltin(IV)] was synthesized by the reaction of (PhCH2)3SnCl with 2,6‐pyridine dicarboxylic acid in 1:1 molar ratio in methanol solution. The structure was characterized by elemental analysis, IR and 1H NMR spectra, and the crystal structure was determined by X‐ray single crystal diffraction analysis. The crystal belongs to monoclinic space group P21/n, a =0.96250(19) nm, b = 1.0947(2) nm, c = 1.9965(4) nm, β = 92.31(3)°, Z = 2, V = 2.1019(7) nm3, Dc = 1.574 g/cm3, μ = 1.248 mm?1, F(000)=1000, R1 = 0.0675, wR2 = 0.0836. In the crystals of the complex, each tin atom is seven‐coordinated in a distorted bipyramidal structure.  相似文献   

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