Synthesis and Crystal Structure of a Cu(Ⅱ) Complex with Reduced Schiff-base N-(2-Hydroxybenzyl)-D,L-alanine and 4,4'-Bipyridine

A new complex [Cu2（sala）2（H20）2（4,4＇-bipy）]＇H20 （sala = N-（2-hydroxybenzyl）- D,L-alaninate, 4,4＇-bipy = 4,4＇-bipyridine） has been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. The complex crystallizes in monoclinic system, space group C2/c with a = 42.44（3）, b = 10.416（8）, c = 15.487（13） ./k, fl = 97.455（14）°, C30H36Cu2N4O9, Mr = 723.71, V = 6789（9） A3, Dc = 1.416 g/cm3, Z = 8, F（000） = 2992, μ（MoKa） = 1.308 mm-1, R = 0.0493 and wR = 0.1004 for 4878 observed reflections （I 〉 2σ（I））. Structural analysis shows that each copper（II） atom displays a distorted square-based pyramidal coordination geometry with two oxygen atoms and one nitrogen atom from one N-（2-hydroxybenzyl）-D,L-alaninate, one nitrogen atom from 4,4＇-bipyridine ligand and one water molecule. 4,4＇-Bipyridine ligand bridges two Cu（II） ions to form a dinuclear compound. The molecular structure is extended into a one-dimensional wavy chain through hydrogen bonds. These 1D chains are further expanded into 2D networks through hydrogen bonds.

Synthesis and Crystal Structure of a New Lanthanum(III) 4-Cyanobenzoate Complex

A new dinuclear La（Ⅲ） complex [La2（4-cba）4[H（4-cba）2]2（phen）2（H2O）4] （4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline） 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by singlecrystal X-ray diffraction. Crystallographic data： C88H58La2N12O20, Mr = 1881.28, triclinic P1, a = 7.518（3）, b = 17.033（6）, c = 17.551（6）A, α = 115.333（4）, β = 92.9910（10）, γ = 99.366（5）°, V = 1985.3（12）A^3, Z = 1, Dc = 1.574 g/cm^3, F（000） = 944 μ = 1.145 mm^–1, the final R = 0.0281 and wR = 0.0686 for 6708 reflections with Ⅰ 〉 2σ（I）. In 1, two nine-coordinated La（Ⅲ） ions are connected by two 4-cba ligands in a syn-syn bidentate coordination mode, and the other six 4-cba ligands terminate the La（Ⅲ） ions, resulting in an isolated dinuclear structure. Two different types of intramolecular hydrogen bonds, asymmetrical O-H…O and symmetrical O…H…O, exist in the crystal. The title complex molecules are connected through hydrogen bonds and weak π-π stacking interactions to generate a 2-D layered network. The thermogravimetric analysis of 1 has also been discussed.

Synthesis and Crystal Structure of a Lanthanum(Ⅲ) Complex with Chelidamic Acid

A new lanthanum complex, （H3O）2[La（C7H3NO5）2（H2O）212.3（H2O） or （HaO）E[La（HChel）2（HEO）E]2.3（H2O） 1 （H3Chel = 4-hydroxypyridine-2,6-dicarboxylic（chelidamic） acid）, has been prepared by the hydrothermal reaction, and its crystal structure was determined based on single-crystal diffraction data. Compound I crystallizes in triclinic, space group Pi with a = 9.6939（19）, b = 10.176（2）, c = 11.502（2）A, α = 111.52（3）, β = 93.74（3）, γ = 103.33（3）°, V = 1013.0（3）A3, Dc = 1.912 g/cm3, Z = 1, Mr = 1166.40, p = 2.188 mm-1, 2（MoKa） = 0.71073 A and F（000） = 574. The final R = 0.0342 and wR = 0.0737 for 4080 observed reflections with I 〉 2σ（I）, and R = 0.0429 and wR = 0.0772 for all data. Compound 1 contains two lanthanum ions, four chelidamic acid ligands, four coordinated water molecules, two hydroniums, and three discrete water molecules. The LaⅢ atom is ten-coordinated by four oxygen and two nitrogen atoms from two tridentate chelating chelidamic acid ligands, two carboxylic oxygen atoms from an adjacent chelidamic acid ligand and two coordinated water molecules, leading to a distorted dodecahedral geometry. A three-dimensional network is formed by H-bonds.

Synthesis and Crystal Structure of a Tetranuclear Carboxylate-bridged Lanthanum(III)-Zinc(II) Complex [La_2Zn_2(m-CNC_6H_4COO)_(10)(Py)_2(C_2H_5OH)_2]

The title complex was prepared from self-assembly reaction of La（NO3）3(6H2O, Zn（NO3）2(6H2O, m-cyanobenzoic acid （m-CNC6H4COOH） and pyridine （Py） in refluxing ethanol and its structure was determined by single-crystal X-ray diffraction. Crystallographic data: C94H62N12La2O22Zn2, Mr = 2120.12, triclinic space group P, a = 13.2219（5）, b = 13.2713（5）, c = 14.1987（6） ?, (???69.156（1）, ( = 84.034（1）, ( = 89.400（1） (, V = 2314.9（2） ?3, Z = 1, Dc = 1.521 g/cm3, F（000） = 1060, ( (MoK（） = 14.94 cm－1, the final R = 0.043 and wR = 0.117 for 6381 unique reflections with I > 2(（I）. Crystal structure determination shows that the neighboring lanthanum（III） and zinc（II） ions are bridged by three bidentate m-cyanobenzonate ligands in the syn-syn fashion to form a pair of dinuclear [LaZn（m-CNC6H4COO）3（Py）（C2H5OH）] subunits, being linked together by two bidentate and two tridentate m-cyanobenzonate groups in the syn-syn and syn-anti modes, respectively, to construct a tetranuclear La-Zn complex [La2Zn2（m-CNC6H4COO）10（Py）2（C2H5OH）2].

Synthesis,Crystal Structure and Fluorescent Property of a Lanthanum(Ⅲ) Complex Coordinated with Quinolinyloxy Acetamide Ligand

A novel lanthanum（III） complex, [LaL2（NO3）3].H2O （1） based on L （L = N-（na- phthalene-l-yl）-2-（quinolin-8-yloxy）acetamide）, was synthesized and characterized by X-ray diffraction. The crystal of I belongs to the monoclinic system, space group C2c with Mr= 1017.69, a = 25.1438（17）, b = 13.5950（9）, c = 18.2349（12） A, β= 132.4980（10）° V= 4595.8（5） A3, Z= 4, Dc = 1.471 Mg/m3, F（000） = 2056,μ= 1.004 mm-1, R = 0,0588 and wR = 0.1402. The central La（lI1） ion is coordinated to four oxygen atoms, two nitrogen atoms from two independent acetarnide ligands and six oxygen atoms from three nitrate anions, possessing a distorted icosahedron coordination geometry. In the crystal of 1, intermolecular N-H……O hydrogen bonds linked the molecules into chains along the c axis. In solid state and CH3CN solution, complex 1 exhibits stronger fluorescent emission than the ligand L.

Synthesis and Crystal Structure of an Unusual Dodecacoordinated Lanthanum Complex by Phenanthroline and Nitrate (phenH)_2[La(NO_3)_5(phen)]·CH_3OH

Lanthanum complex （phenH）2[La（NO3）5（phen）]·CH3OH （1, phen=phenanthroline） was synthesized and characterized by single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/c with a=20.3040（3）, b=10.7091（1）, c=19.0771（2）, β=102.090（1）°, V=4056.07（8）3, Z=4, Dc=1.676 g/cm3, μ= 1.142 mm-1, F（000）=2056, the final R=0.0346 and wR=0.0793 for 9981 （Rint=0.0358） independent reflections. The mononuclear complex 1 consists of four parts： two phenH＋ cations formed by the protonation of phen, one complex anion [La（NO3）5（phen）]2-, and one solvent methanol molecule. The complex anion contains one phen and five nitrate ligands which both chelate the center La（III） ion, adopting a distorted twelve-coordinated icosahedral geometry. The cations, anion and solvent molecule are linked together by hydrogen bonds. One of the protonated phenanthrolines （phenH＋） acting as cation connects to the anion via N–H…O hydrogen bond directly, and the other one links to the anion through an intermediate solvent CH3OH via N–H…O and O–H…O hydrogen bonds. By the plentiful additional weak C–H…O intermolecular hydrogen bonds, the compound molecules construct a two-dimensional layer structure.

Hydrothermal Synthesis,Crystal Structure and Properties of a Lanthanum(Ⅲ) Complex Based on a N,O-Donor Ligand

A novel metal-organic complex [La（o-NCP）3]n （o-HNCP = 2-（2-carboxyphen- yl）imidazo（4,5- f）（1,10）-phenanthroline） has been hydrothermally synthesized and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The complex crystallizes in triclinic, space group P1 with a = 9.898（2）, b = 16.193（3）, c = 16.909（3） A, a = 67.68（3）, β = 80.85（3）, y = 78.78（3）°, V= 2448.2（8） A3, Z = 2, Mr = 1156.9, Dc = 1.569 g/cm3,μ = 0.71073 A, F（000） = 1164, GOOF = 1.065, the final R = 0.051 and wR = 0.123 for 8539 observed reflections with I 〉 2o（I）. The complex exhibits a one-dimensional double chain structure. The adjacent chains are further connected by N-H...N hydrogen bonds which help to form a two-dimensional suprarnolecular architecture. Furthermore, the complex exhibits excellent thermal stability and luminescent property.

Synthesis and Structure of a Novel Tetranuclear Erbium( Ⅲ) Complex with α-Alanine[Er_4(HAla)_6·(μ_3-OH)_4(H_2O)_8](ClO_4)_8·3H_2O

The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1.319 4(4) nm, c=1.950 2(4) nm, α=90.597(14)°, β= 93.998(11)° , γ=94.093(13)°, V=3.344 1(12) nm3, Z=2, the final R indices are R 1= 0.065 4 , wR 2=0.126 2 respectively. The complex contains a novel tetranuclear cluster cation with four Er 3+ ions connected by four μ 3OH ions and six bridging carboxyl groups. Each erbium ion is coordinated by three μ 3OH, three carboxylic oxygen atoms from three αalanine and two oxygen atoms from water molecules, forming a squareantiprismatic coordination polyhedron.

Synthesis and Crystal Structure of Lanthanum Nitrate with Methyl-2-pyridyl Ketone Benzoyl Hydrazone

A novel La complex with methyl-2-pyridyl ketone benzoyl hydrazone has been synthesized and determined by single crystal X-ray diffraction. The crystal is monoclinic with space group C2/c, a =1 7081(3) nm, b =1 5660(3) nm, c =1 3512(3) nm, α=90 00°, β=94 39(1)°, γ=90 00°, V =3 6037(12) nm 3, Z =4 . The complex is a ten-coordinated one with a lanthanum ion surrounded by a N 4O 6 set. The crystal structure is stabilized by hydrogen bonds between water molecules and NO - 3 anions.

Hydrothermal Synthesis and Crystal Structure of Lanthanum Orotate Supermolecule with A Honeycomb Structure Constructed from Mononuclear Molecules via Hydrogen Bonds

A new complex of lanthanum orotate [La（C5H3N2O4）2（OH）（H2O）6 ]·2（C5H4N2O4）·9H2O was synthesized using a hydrothermal method. The crystal structure was determined with help of single crystal X-ray diffraction analysis. The complex crystallized in orthorhombic system, Cmc2（1） space group. In the complex, the center lanthanum （Ⅲ） ion was nine-coordinated with coordination geometry of a distorted monocapped square antiprism, in which two of the nine coordinated oxygen atoms were from two orotate ligands in a monodentate mode, one oxygen atom from a hydroxyl, and the others from six coordinated water molecules. The mononuclear complex [La（C5H3N2O4）2（OH）（H2O）6 ]·2（C5H4N2O4）·9H2O was linked through the hydrogen bonds into an infinite supermolecular honeycomb structure.

Rare Earth Complexes of Aminopolycarboxylic Acid Ⅱ.Synthesis and Structure of Lanthanum Complex of Dipicolinic Acid

Complexes of the general formula,(Me_4N)_2[(Ln(HDPA)_2(DPA)]·Cl,have been synthesized,where Ln=La,Ce,Pr,Nd,Sm and H_2DPA=dipicolinic acid.Among them,the crystal structure of the La complex has been determined by a four-circle X-ray diffractometer to a final R value of 0.080.The crystal is orthorhombic,space group Pccn with a=1.0321(1),b=1.4951(2),c=2.0766(6)nm,V=3.2044(9)nm^3,and Z=4.The rare earth ion is nine coordinated to forming a tortuous tricapped trigonal prism.

Crystal Structure of Tris-（dimethoxyphosphato） Lanthanum （Ⅲ） Coordination Polymer {La PO2（OCH3）2 3} n

The crystal structure of tris-(dimethoxyphosphato) lanthanum(Ⅲ) coordination polymer, {La[PO2(OCH3)2]3}n, has been determined from single crystal X-ray diffraction data. The crystal is triclinic, space group P1 with a= 9. 625 (2) , b=10. 418(2) , c=11. 352(4) A, ai13.05(2) ,β=107. 33(2) ,γ=62. 22 (2)°and Z=2, (La[PO2(OCH3)2]3, V= 917. 4(4) A, Dc= 2. 466 gcm-3,λ(MoKα) =0. 71073 A, μ=26. 64 cm-1, F(000) =504, final R=0. 0625 for 4839 unique reflections with I】3σ(Io). The lanthanum ions are coordinated in a distortional octahedral arrangement to six oxygen atoms from six bridging ligands with a mean neighbour O-La-O angle of 90. 8° and a mean La-O distance of 2.437 A.The polymer networks of metal ions are linked by phosphate bridges, and the adjacent network layers are held together only by Van der waals interaction.

Preparation and Crystal Structures of LaCl_3（12－crown－4）（MeOH）and［LaCl_3（phen）_2（H_2O）］·MeOH

The interaction of lanthanum(Ⅲ) chloride with 12-crown-4 in MeCN/MeOH mixed solvent produces an anhydrous complex,LaCl3(12-crown-4)(MeOH)(complex Ⅰ),C9H20O5LaCl3(Mr= 453.6),in which the La(Ⅲ) ion is 8-coordinated by three Cl anions,four oxygen atoms from a crown ligand and a methanol oxygen atom,the complex molecules were connected into a dimer by two O(MeOH)…Cl hydrogen bonds.Reaction of complex Ⅰ with phen(1,10-phenanthroline) gives the crystallization of[LaCl3 (phen)2(H2O)]·MeOH(complex Ⅱ),C25H22O2N4LaCl3(Mr= 655.8) in which the crown ligand is totally replaced by two phen molecules.Cell parameters for the two complexes are a= 9.389(3)[13.228 (5)],b=11.382(4)[10.767(3)],c=7.542(3)[18.520(6) ];α=94.32(3)[90.0],β=102.10(2)[102.01(3)],γ=91. 83(3)[90. 0]°with space group P1[P21/α];V=784.5(5)[2580(1)3,Z=2[4];μ(MoKα)=32.8[20. 2]cm-1;F (000)=444[1296];R=0.042[0.045];Rω=0.044[0.036] for 2398 [2345] observed reflections withⅠ>3σ(Ⅰ).The La(Ⅲ) ion in complex Ⅱ is 8-coordinated by three Cl anions,four N atoms of two phen molecules and one water molecule.The methanolmolecule forms a hydrogen bond with Cl(3) atom.

Synthesis and Crystal Structure of trans(N)-(1,10-Phenanthroline)-bis (DL-Al aninato)-Cobalt( Ⅲ ) Chloridetrihydrate

The title compound was synthesized by the reaction of cis-[Co(phen)2Cl2]Cl·3H2O with DL-alanine at pH = 8, and isolated using a column chromatographic method. Its crystal structure was determined. The crystal structure belongs to mono-clinic system, space group P21/c, with a = 0. 9549(6) nm, b=2.3746(8) nm, c= 1.0782(4) nm, β=114.13(3)°? Z = 4, Dc= 1. 50 g/cm3. The final refinement converged to R = 0. 047 for 3246 independent observed reflections. In the octahedral coordination sphere formed by the cobalt atom and the coordinate atoms, N, O of DL-alan-inato ligands are in the configuration of trans-N ,N form.

Synthesis and Structure of Polynuclear Complex [La(bphsb)_2(NO_3)_3]_n

The polynuclear complex, [La(bphsb) 2(NO 3) 3] n (bphsb=1,4 bis(phenylsulfinyl)butane) were obtained. The structure of the complex consists of ten coordinated metal ions linked up with six O atoms of the three bidentate nitrates and with four O atoms of the four bphsb ligands. The coordination polyhedron of the La 3+ may best be described as distorted bicapped square antiprism. The bphsb ligands act as bridges that join two neighbouring lanthanum ions to give polymeric chains. Each chain contains 18 membered macrocyclic rings with two La atoms. In the complex, the bphsb ligands adopt meso stereoisomer in which sulfur atoms are chiral, and the absolute configurations of the atoms are RS.

Synthesis and Structural Characterization of a Cyano-bridged 1-D Lanthanum(Ⅲ)-iron(Ⅲ) Complex [La(DMSO)_5(H_2O)](μ-CN)_2[Fe(CN)_4]·H_2O

ABSTRACT A new lanthanumm-ironm complex [La（DMSO）5（H2O）]（μ-CN）2[Fe（CN）4]·H2O 1 （DMSO = dimethylsulfoxide） has been prepared by a facile approach, ball-milling method, and characterized by X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 9.7125（3）, b = 21.5336（7）, c = 14.3804（5）A, β = 93.242（3）°, C16H34FeLaN60O7S5, Mr= 777.55, V = 3002.8（2）A^3, Z = 4, Dc = 1.720 g/cm^3, S = 1.053, μ（MoKα） = 2.278 mm^-1, F（000） = 1564, R = 0.0490 and ωR = 0.1270. The crystal structure analysis of 1 reveals a slightly distorted squareantiprism eighffold-coordinated La（Ⅲ） ion and a 1-D zigzag chain structure extending through the Fe-CN-La-NC-Fe linkages. The [La（DMSO）5（H2O）]（μ-CN）2[Fe（CN）4] species are held together via hydrogen bonds to form a three-dimensional framework.

Crystal Structure of[La(NO_3)_3(12-crown-4)-(H_2O)](12-crown-4)

The crystal structure of crown ether-hydrogen bonded complex,[La(NO3)3 (12-crown-4) ( H2O)] (12-crown-4) has been determined by X-ray method. The title complex C16H34LaN3O18 (Mr=695. 5) crystallized in orthorhombic Pnma with a=23. 495(8), b=13. 603(5),c=8. 474(3); V=2706(1); Z=4 ; Dc=1. 71 g/cm3; F(000)=1408, μ=17. 0 cm-1 (MOKα). The final R=0. 052 and Rw= 0. 054(unit weight) for 1367 observed reflections. The La( Ⅲ) ion is 11-coordinated by three nitrale anions, four oxygen atoms from a crown ligand and one O atom of a water molecule. The other crown molecule is hydrogen bonded wilh the coordinated water molecule. The imposed mirror plane in the structure made both crown ligands and one of nitrate groups severely disordered.

Synthesis and Structure of a Novel Tetranuclear Erbium(Ⅲ) Complex with L-Proline(HPro)[Er_4(HPro)_4(Pro)_2·(μ_3-OH)_4(H_2O)_7](ClO_4)_6·6H_2O

The title complex was synthesized in an aqueous solution and its crystal structure was determined by Xray diffraction. The crystal crystallizes in a triclinic system, space group P1 with a= 1.306 3(2) nm , b=1.319 4(4) nm, c=1.950 2(4) nm, α=90.597(14)°, β= 93.998(11)° , γ=94.093(13)°, V=3.344 1(12) nm3, Z=2, the final R indices are R 1= 0.065 4 , wR 2=0.126 2 respectively. The complex contains a novel tetranuclear cluster cation with four Er 3+ ions connected by four μ 3OH ions and six bridging carboxyl groups. Each erbium ion is coordinated by three μ 3OH, three carboxylic oxygen atoms from three αalanine and two oxygen atoms from water molecules, forming a squareantiprismatic coordination polyhedron.

Preparation and Crystal Structures of LaCl3（12－crown－4）（MeOH）and［LaCl3（phen）2（H2O）］·MeOH

The interaction of lanthanum(Ⅲ) chloride with 12-crown-4 in MeCN/MeOH mixed solvent produces an anhydrous complex,LaCl3(12-crown-4)(MeOH)(complex Ⅰ),C9H20O5LaCl3(Mr= 453.6),in which the La(Ⅲ) ion is 8-coordinated by three Cl anions,four oxygen atoms from a crown ligand and a methanol oxygen atom,the complex molecules were connected into a dimer by two O(MeOH)…Cl hydrogen bonds.Reaction of complex Ⅰ with phen(1,10-phenanthroline) gives the crystallization of[LaCl3 (phen)2(H2O)]·MeOH(complex Ⅱ),C25H22O2N4LaCl3(Mr= 655.8) in which the crown ligand is totally replaced by two phen molecules.Cell parameters for the two complexes are a= 9.389(3)[13.228 (5)],b=11.382(4)[10.767(3)],c=7.542(3)[18.520(6) ];α=94.32(3)[90.0],β=102.10(2)[102.01(3)],γ=91. 83(3)[90. 0]°with space group P1[P21/α];V=784.5(5)[2580(1)3,Z=2[4];μ(MoKα)=32.8[20. 2]cm-1;F (000)=444[1296];R=0.042[0.045];Rω=0.044[0.036] for 2398 [2345] observed reflections withⅠ】3σ(Ⅰ).The La(Ⅲ) ion in complex Ⅱ is 8-coordinated by three Cl anions,four N atoms of two phen molecules and one water molecule.The methanolmolecule forms a hydrogen bond with Cl(3) atom.

La^(3+)取代的纳米尺寸砷钨氧簇的合成、晶体结构及光催化性质研究

本文基于自组装原理,以Na_(2)WO_(4)·2H_(2)O、亚砷酸钠和LaCl_(3)·6H_(2)O为主要原料,采用一锅法将稀土金属La~Ⅲ与缺位结构的多钨氧簇构筑单元结合得到了一例新型稀土基砷钨氧簇合物,并借助单晶X射线衍射、X射线粉末衍射(PXRD)、傅里叶红外光谱(IR)等手段确认了其结构和组成。单晶X射线衍射结果表明:该配合物属于单斜晶系,C2/c空间群,晶胞参数为a=3.59556(14)nm,b=1.22248(4)nm,c=2.24734(9)nm,β=117.1170(10)°,V=8.7923(6)nm^(3),Z=4,其分子式为[(CH_(3))_(2)NH_(2)]_(8)H_(3.56)[{LaO(H_(2)O)_(2)}{WO(H_(2)O)}{W_(0.24)(H_(2)O)_(2)}{AsW_9O_(33)}_(2)]。在该化合物中,聚阴离子簇[{LaO(H_(2)O)_(2)}{WO(H_(2)O)}{W_(0.24)(H_(2)O)_(2)}{AsW_9O_(33)}_(2)]~(11.56-)具有三明治结构,可以看作是由两个{AsW_(9)O_(33)}单元夹心1个{LaO(H_(2)O)_(2)}片段、1个{WO(H_(2)O)}组分和1个{W_(0.24)(H_(2)O)_(2)}片段组成。本文进一步探究了该化合物对于罗丹明-B的催化降解性质,结果表明,在300 W的汞灯照射条件下,该化合物表现出了良好的光催化活性,降解效率为74%。