CRYSTAL STRUCTURE OF DI - NITRATOBIS(ETHYLCAPROLACTAM)URANYL(Ⅱ) UO_2[CH_2(CH_2)_4CONC_2H_5]_2(NO_3)_2

The crystal structure of Di-nitratobis(ethylcaprolactam)uranyl(Ⅱ) UO_2[CH_2(CH_2)_4CONC_2H_5]_2(NO_3)_2 was established by a single-crystal X-ray diffraction study.It is triclinie, space group P1, with a=7.171(2), b=8.655(3), c=10.182(5)A, α=78.27(3), β=70.63(3), γ=81.76(3)°, V=581.7(4)A~3, Z=l, Dc=1.94 g.cm~(-3).Final R value is 0.0218.The result reveals that uranyl ion is coordinated to six oxygen atoms, two of them are from two carbonyl groups of ethylcaprolactam and the other four are from two nitrate groups.     

A Hexanuclear Cobalt Cluster with Tetracubane-like Topology: Synthesis,Structure and Magnetic Properties

One hexanuclear cobalt cluster [Co_2~ ⅢCo_4 ~Ⅱ(L)_4(CH_3 COO)_2(MeO)_4]·MeOH(1) was synthesized by the reaction of H_2L(H_2L=2-((2-hydroxy-4-methoxy-benzylideneamino)methyl)phenol) and Co(OAc)_2·4 H_2O in MeOH under solvothermal conditions. Complex 1 crystalizes in the triclinic space group ■ with a = 14.397(3), b = 16.625(3), c = 18.992(4) ?, α = 109.47(3)°, β = 99.24(3)°, γ = 112.37(3)°, Dc = 1.464 g/cm3, Z = 2, V = 3741.7(2) ?3, the final R = 0.0781 and w R = 0.1436 for 13051 observed reflections with I 2σ(I). In the structure of 1, two cobalt ions are in 3+ oxidation states and four cobalt ions are in 2+ valence states. The six cobalt atoms are held together by six phenolate oxygen atoms from four L2– ligands, four oxygen atoms from two chelating acetates and four μ3-O atoms from four Me O– groups. The six cobalt atoms are located at six corners of four defective cubanes. Thus, complex 1 displays tetracubane-like topology. Solid-state dc magnetic susceptibilities were measured for 1 in the 2.0～300 K range. Antiferromagnetic interactions were determined for 1.     

CRYSTAL STRUCTURE OF A HETERONUCLEAR LANTHANIDE COMPLEX OF ERBIUM-YTTRIUM AND GLYCINE[ErY(GlY)_6(H_2O)_4](ClO_4)_65H_2O

The title complex [ErY(Gly)_6(H_2O)_4](ClO_4)_6 5H_2O has been synthesized.Its crystalstructure has been determined by X-ray diffraction method.The crystal is triclinic with space groupP1.The unit cell parameters are as follows:a=11.518(4),b=14.105(7),c=15.530(6) ,α=96.61(3),β=102.74(3),γ=105.70(3)°,V=2327.7(17) ~3,Z=2,Dc=2.091g/cm~3.The structure has been refinedto a final R of 0.0785.The crystal is an infinite chain complex,in which four carboxyl groups fromglycine molecules bridge the Er(Ⅲ)and Y(Ⅲ)ion,other two carboxyl groups bridge two adjacentEr(Ⅲ)or two Y(Ⅲ)ions.     

Syntheses of (C_5H_9C_5H_4)_2LnCl(THF)_n (Ln=Nd, Sm, Er, Yb) and crystal structure of [(C_5H_9C_5H_4)_2-LnCl(THF)_n]_2(Ln=Sm, n=1; Ln=Er, n=0)

Reactions of lanthanoid trichlorides with sodium cyclopentylcyclopentadienyl in THFafford bis(cyclopentylcyclopentadienyl) lanthanoid chloride complexes (C_5H_9C_5H_4)_2LnCl(THF)_n (Ln=Nd, Sm, n=1; Ln= Er, Yb, n= 0). The compound [CP'_2SmCl(THF)]_2 (2) (Cp' =cyclopentylcy-clopentadienyl) crystallizes from mixed solvent of hexane and THF in monoclinic space group P_2_1/cwith a = 11.583 (3), b = 23.019(6), c = 8.227 (2), β= 90.26 (2)°, V= 2194 (1)~3, D_c= 1.59 g/cm~3.μ= 28.6 cm~(-1), F(000) = 1060, Z= 2 (dimers). Its crystal molecule is a dimer with a crystallographicsymmetry center. The central metal atom Sm is coordinated to two Cp' rings, two bridging chlorineatoms and one THF forming a distorted trigonal bipyramid. The crystal of [Cp'_2ErCl]_2 (3) belongs tothe triclinic space group P with a = 11.264 (2), b= 13.296(5), c = 14.296(6), a = 96.99 (3), β=112.47(2), γ= 102.78(2)°, V= 1865(1)~3, D_c= 1.67 g /cm~3, μ= 48.0 cm~(-1), F(000) = 924, Z = 2 (dimers).The molecule is a dimer consisting of two Cp'_2 ErCl species bridged by two Cl atoms. The centralmetal atom Er is coordinated to two Cp' rings and two bridging chlorine atoms forming a pseudo-tetrahedron. All these complexes are soluble in THF, DME, Et_2O, toluene and hexane.     

STUDY ON SYNTHESIS, STRUCTURE AND COMPLEXATION CHARACTERISTIC OF UO_2Cl_4(DCH 18C6·H_3O)_2*

The title compound was synthesized by extracting nranylchloride in HC1 system using dicyclohexyl-18-crown-6 as extraction agent. The absorption peaks 1090 cm~(-1) and 912 cm~(-1) in IR spectrum result from frequence red-shift of anti-symmetric stretch vibration of C—O—C of crown ring and [OUO] group, respectively.X-ray diffraction analysis results in its crystallographic parameters: triclinic system, space group P; a=10.183(3), b=10.606(3), c=12.850(6), α=72.09(3), β=85.97(4), γ=86.14(2)°, V=1315.7, z=1. The structure was solved by heavy atom method. Structure refinements converged to final R=0.062, R_w=0.061. U atom is situated on the symmetry center and coordinated by four chlorine atoms and two oxygen atoms to form a square bipyramid coordination polyhedron. The H_3O~+ group is embedded in the crown ring and connected with three crown oxygen atoms via hydrogen bonds.     

Synthesis,Crystal Structure and Photoluminescence of a One-dimensional Zinc(Ⅱ)Coordination Polymer with Substituted Terpyridine

<正>The title compound,[Zn(4-pytpy)(NO_3)_2](4-pytpy=4'-(4-pyridyl)-2,2':6',2"- terpyridine)1,has been synthesized by the solvothermal reaction of Zn(NO_3)_2·6H_2O with 4-pytpy in CH_3OH solution.It crystallizes in the triclinic system,space group P_1~-with a=8.358(6),b= 11.121(8),c=11.374(8)(?),α=74.226(11),β=74.532(11),γ=83.085(12)°,M_r=499.74,V= 979.3(12)(?)~3,Z=2,D_c=1.695 g/cm~3,F(000)=508,μ=1.309 mm~(-1),the final R=0.0547 and wR= 0.1588.X-ray crystal structure analysis revealed that the Zn~Ⅱis hexa-coordinated by two oxygen atoms from two nitrate groups and four nitrogen atoms,three of which are from the tridentate domain of one 4-pytpy and the other from the monodentate domain of another 4-pytpy.4-pytpy as a bridging ligand connects Zn~Ⅱinto a one-dimensional coordination polymer.     

Synthesis and Structure of Dibenzoyl-bissemicarbazone Neodymium(Ⅲ) Perchlorate

A new Schiff base Dibenzoyl-bissemicarbazone C15H16N6O2(L) and its complex with neodymium(Ⅲ ) perchlorate [NdL2(H2O)2](ClO4)3 were synthesized. The crystal and molecular structure of the title complex were determined by single crystal X-ray diffraction. The crystal is monoclinic and conforms to space group P. with cell constants a=10. 893(2) A, b= 12. 118(3) A , c=22. 494(5) A , β=89. 86(3)% V = 2969.19A3. The final standard deviation R=0. 0919. In the complex Nd is coordinated by four nitrogen and six oxygen atoms, of which four nitrogen and four oxygen atoms are provided by two neutral ligands L, and the other two oxygen atoms are provided by two water molecules, forming a ten-coordinated complex cation, which the perchlorate groups exist in the outer sphere. The coordination polyhedron takes a bicapped anti-square prism arrangement. That the average bond length of Nd-N is 2. 735 A indicates that the coordination of N in groups to Nd( Ⅲ ) is very weak.     

3D Bi(Ⅲ)-La(Ⅲ)异金属配位聚合物的合成、结构和热稳定性

A new Bismuth(Ⅲ)-Lanthanum(Ⅲ) heterobimetallic polymer complex,{[(H_2O)_5La(μ_4-edta)Bi(NO_3)_2]·3H_2O}_n(edta=diaminetetraacecarboxylate),has been hydrothermally synthesized and characterized by elemental analysis,FT-IR,and X-ray diffraction single crystal structure analysis.It crystallizes in the monoclinic system,with space group P2(1)/n,a=1.27395(5)nm,b=0.82608(4) nm,c=2.38819(11) nm,β=104.9000(10)°,V=2.42879(19) nm~3,Z=4,Dc=2.438 g·cm- 3,μ=9.077mm~(-1),F(000)=1678,R_1=0.0343,wR_2=0.0906.In this complex,Bi atom is coordinated by four carboxyl O atoms from a single edta~(4-) anion.La atom is bonded to four O atoms from four bridging carboxyl O atoms belonging to four different edta~(4-) anions and five O atoms from five H_2O molecules.Bi atoms and La atoms are linked by bridged edta~(4-) anions,resulting into a novel infinite 3D network structure.TG-DSC and IR indicate that thermal decomposition proceeds in several stages,dehydration,pyrolysis of ligand,and finally decomposition of salt,and the residue is composite oxide based on δ-Bi_2O_3 at the temperature of 600℃.     

配合物[Tb(p-ClBA)_3(phen)]_2的结构和性能(英文)

Terbium p-chlorobenzoate complex with 1,10-phenanthroline, [Tb( p-ClBA)_3phen]_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)_3phen]_2 is quite stable to heat. CCDC: 221921.     

Synthesis and Structure of a NovelTetranuclear Erbium( Ⅲ) Complex with α-Alanine [Er4(Hala)6·(μ3-OH)4(H2O)8](ClO4)8·3H2O

The title complex was synthesized in an aqueous solution and its crystal structure was determined by X-ray 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 R1=0.065 4, wR2=0.126 2 respectively. The complex contains a novel tetranuclear cluster cation with four Er3+ ions connected by four μ3-OH ions and six bridging carboxyl groups. Each erbium ion is coordinated by three μ3-OH, three carboxylic oxygen atoms from three α-alanine and two oxygen atoms from water molecules, forming a square-antiprismatic coordination polyhedron.     

Syntheses,Structures and Properties of Two New Coordination Polymers with Flexible Ligands as Linkers

Two new coordination polymers,[ZnL1]_n(1,H_2L1 = 5-(4-pyridyl)-methoxyl isophthalic acid) and[Ni(L2)_2(H_2O)_4]_n(2,HL2 = 4-(pyridin-4-ylmethoxy)benzolic acid),have been synthesized and characterized by elemental analysis,PXRD,IR spectra,and single-crystal X-ray diffraction.Compound 1 has a three-dimensional framework constructed by 6-bridged L1~(2-) anions connecting the Zn_2(O_2C)_4 paddlewheel-like units.Compound 2 contains a mononuclear molecular unit,and the central nickel atom adopts a slightly distorted octahedral geometry by two nitrogen atoms from different L2~- ligands and four oxygen atoms from water molecules.These molecular units link each other via four types of O-H…O hydrogen bonds to form an extended three-dimensional(3D) supramolecular network.The thermal and photoluminescent properties of 1 and 2 have also been investigated.     

A new route to prepare the mixed oxo-ethylidynecapped trinuclear tungsten(Ⅳ)cluster and the crystal structure of H_2Na_3[W_3O(CCH_3)(O_2CCH_3)_6(H_2O)_3][H_2W_(12)O_(40)]·13.5H_2O

The synthesis and the structural characterization of the title compound H_2Na_3[W_3O(CCH_3)-(O_2CCH_3)_6(H_2O)_3][H_2W_(12)O_(40)]·13.5 H_2O are described.It is known that the mixed oxo-ethylidyne-capped tritungsten cluster can be obtained by Zn dust reduction of Na_2WO_4·2H_2O in acetic anhydride.The title compound has been characterized by X-ray diffraction,UV/VIS and ~1H NMR spectra.The tungsten atoms in the cluster cation and anion are in the oxidation states of W(IV)and W(VI)respectively.The crystal is rhombohedral with the space group R32,a=17.058(3),c=49.665(9),γ=120°,V=12516(9)~3,Z=6,final R=0.037 for 2071 reflections with I≥3σ(I).Boththe cluster cation and anion have a C_3 symmetry.The important interatomic distances in angstroms forthe cluster cation are:W—W,2.730(2);W—μ_3-O,2.00;W—O(carboxyl),2.12;W—O_t,2.18(2).     

Synthesis,crystal structure,magnetic properties and second harmonic generation of a new noncentrosymmetric coordination compound:Triaqua(4-amino-6-methoxypyrimidine) cuprate(Ⅱ)sulfate

The chemical preparation, crystal structure and infrared spectroscopic characterization of the triaqua(4-amino-6-methoxypyrimidine) cuprate(II) sulfate, [Cu(C_5H_7N_3)(H_2O)_3]SO_4, is reported. The compound crystallizes in the noncentrosymmetric orthorhombic space group P2_12_12_1 with lattice parameters a = 7.9025(3), b = 11.1189(4), c = 12.9720(4) , V = 1139.81(7) ~3 and Z = 4. The Cu(II) cation is fivecoordinated, in an early half-way between square pyramidal and trigonal bipyramidal fashion, by two nitrogen atoms of the 4-amino-6-methoxypyrimidine ligand and three water oxygen atoms. In the atomic arrangement, the organic ligands and the 5-connected Cu centers are linked with each other to give a 1-D corrugated hybrid chain running along the b-axis direction. The chains are interconnected by the SO_4~(2-) anions via O–H...O, O–H...S, C–H...O and N–H...O hydrogen bonds to form layers spreading parallel to the(011) plane. The vibrational absorption bands were identified by infrared spectroscopy. Quantitative measurements of the second harmonic generation(SHG) of a powdered sample at 1064 nm were performed and a relative efficiency of 5.2 times the KDP standard was observed. Magnetic properties were also defined to characterize the complex. Magnetic measurements revealed that this material had a onedimensional antiferromagnetic character. The magnetic parameters were g = 2.11 and 2J/k B = -36 K.     

Syntheses,Crystal Structures and Antibacterial Activities of Schiff Base of Nickel(Ⅱ) and Copper(Ⅱ) Complexes

A new kind of Schiff base HL(HL= 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-Leucine methyl ester) and complexes Ni L′_2·0.75C_2H_5OH·0.25H_2O,Cu L′′2(L′ = 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-leucine ethyl,L′′ = 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-leucine) have been synthesized and structurally determined by X-ray diffraction. For HL: crystal structure determination indicates that there are two independent HLs with different conformations in one asymmetric unit. For complex 1: the Ni(Ⅱ) ion is six-coordinated by two carbonyl oxygen atoms from pyrazolone ring,two nitrogen atoms from different HL′ and two oxygen atoms from L-Leucine ethyl ester to form a distorted octahedral geometry. For complex 2: the Cu(Ⅱ) ion is four-coordinated by one carbonyl oxygen atom from the pyrazolone ring,one nitrogen atom from HL′′,and two different carboxylic oxygen atoms from L-leucine with the same conformation to form a distorted quadrilateral geometry.     

SYNTHESIS, CHARACTERIZATION AND STRUCTURE OF [Co(DBP)_2·3Py]_2·2CHCl_3

The mixed ligand complex of cobalt with dibutylphosphate (HDBP) and pyridine has been synthesized. Elemental analysis yields the result that the formula of this compound is Co(DBP)_2·3Py·CHCl_3 (Py=pyridine). The thermal analsyis, visible spectra and magnetic properties of it have been studied as well. Single crystal structural analysis shows that the crystal is triclinic with space group P and the unit cell parameters are as follows:a=14.490(10), α=90.37(4)°,b=15.721(7), β=96.04(5)°,c=20.109(12), γ=105.63(4)°.The final R factor is 0.0773. Two Co atoms are connected by two bridging DBP groups to form a dinuclear molecule [Co(DBP)_2·3Py]_2 which has a C_s, symmetry. Each cell contains two dinuclear molecules and four chloroform molecules. The cobalt is coordinated in an octahedral arrangement by three oxygen atoms and three nitrogen atoms, of which one oxygen atom comes from a monodentate DBP group, two oxygen atoms from two bridging DBP groups, and the three nitrogen atoms from the three pyridi     

Structures and Photoluminescent Properties of 3D Ho(Ⅲ) and Y(Ⅲ) Complexes with 2,4,6-Pyridinetricarboxylate

Two 3D rare earth coordination polymers {[Ho(ptc)(H_2O)_(2.5)]·0.5 H_2O}n(1) and {[Y2(ptc)2(H_2O)_5]·H_2O}n(2)(H_3ptc = 2,4,6-pyridinetricarboxylic acid) have been synthesized with Ho(Ⅲ) or Y(Ⅲ) chloride and H_3ptc by hydrothermal method. The X-ray structure analyses display the two complexes are isomorphic and crystallize in monoclinic crystal system with P21/n space group for 1 and P21/c space group for 2. Ho(Ⅲ) and Y(Ⅲ) both show two different coordination modes. One is nine-coordinated and forms a distorted tricapped trigonal prism and the other is eight-coordinated to get a distorted bicapped trigonal prism. The ptc3-also shows two different coordination modes by connecting four or three rare earth ions. The photoluminescent properties of 2 show that it can emit blue fluorescence at 440 nm with excitation at 335 nm. The fluorescence lifetime of 2 is 1.64 μs and the absolute fluorescence quantum yield is 10.2%.     

Synthesis,Structure and Characterization of a 3D Chiral Barium Carboxylate Metal-organic Framework Based on TADDOL Ligand

A novel alkaline earth-based chiral metal-organic framework 1 {[Ba_(1.5)L(μ-OH_2)_2(DMF)_2(H_2O)]·DMF·1.5 H_2O}_n was synthesized from C2-symmetric TADDOL-based ligand H_4L and structurally characterized by single-crystal and powder X-ray diffraction, Fourier-transform infrared spectra(FTIR), solid-state circular dichroism(CD) and thermal gravimetric analysis(TGA). 1 crystallizes in monoclinic space group C2 with a = 43.5105(12), b = 9.4781(3), c = 15.5620(4) ?, β = 99.7770(10)o, V = 6324.5(3) ?~3, Z = 2, M_r = 1434.18 g/mol, D_c = 1.506 g/cm~3, F(000) = 2904, GOOF = 1.026, the final R = 0.0358 and w R = 0.0952 for 21747 observed reflections with I 2σ(I). Each Ba3 cluster in 1 is linked by eight ligands and each ligand with one coordination-free carboxyl oxygen, O(5), is coordinated to four Ba_3 clusters to generate a 3D network. In addition, the photoluminescence of 1 and H_4L was also investigated.     

STUDIES ON RARE EARTH COMPLEXES OF QUARTERNARY AMMONIUM SALT——SYNTHESIS AND CRYSTAL STRUCTURE OF TETRAKIS-(TRIMETHYL-HEXADECYL AMMONIUM)DECANITRATO DINEODYMATE,((CH_3)_3C_(16)H_(33)N)_4Nd_2(NO_3)_(10)

A series of binuclear eleven-coordinated rare earth complexes with long chain quarternary ammonium salt have been synthesized. The general formula of the complexes may be represented by((CH_3)_3 C_(16)H_(33)N)_4Ln_2(NO_3)_(10) where Ln is La, Ce, Pr, Nd, Sm, Eu, Ga, Ho, Er or Y. The TG curve, the magnetic moment and the dissociation degree of the Nd complexes in alcoholic solution have been determined.((CH_3)_3C_(16)H_(33)N)_4 Nd,_2NO_3)_(10) was chosen as a representative of the complexes for the crystal structure determination. The crystal is monoclinic with space group P. Each Nd atom is coordinated by four terminal nitrate groups bidentately, and two Nd atoms are connected through two O atoms of the nitrate groups forming binuclear complex. Therefore, each Nd atom is surrounded by eleven oxygen atoms. The average bond length of the eleven Nd-O bond is 2.57, while the Nd-O bond length on the oxygen-bridge is 2.62.     

Synthesis,Structure and Characterization of a New Complex: [Mn(C_6H_(12)N_4)_2(H_2O)_4][Mn(H_2O)_6][SO_4]_2·6H_2O

A novel complex,[Mn(C_6H_(12)N_4)_2(H_2O)_4][Mn(H_2O)_6][SO_4]_2·6H_2O,was synthesized and hexagonal single crystals with centimeter-scale sizes were obtained by the method of solvent evaporation.It was characterized by elemental analysis,infrared spectrum,thermogravimetric analysis and X-ray single-crystal diffraction.The complex belongs to triclinic crystal system,space group P■ with a=9.3390(8),b=13.3520(13),c=16.3207(13)?,α=100.7160(3)°,β=90.1020(10)°,γ=109.9490(5)°,V=1874.9(3)?~3,Z=2,D_c=1.542 g/cm~3,M_r=870.64,μ=0.876 mm~(-1),T=293(2) K,F(000)=916 and S=0.990.The crystal structure determination displayed a distorted octahedral geometry around the manganese atom,which is bound to two nitrogen atoms from hexamethylenetetramine,acting as monodentate ligands,and to four aqua ligands.Variable-temperature magnetic measurements of the complex indicate the presence of weak antiferromagnetic interaction between manganese centers.     

CRYSTAL STRUCTURE OF BIS-ETHYLENEDIAMINE TRITHIOCYANATE OF COPPER(Ⅱ) AND SILVER(Ⅰ) Cu(en)_2Ag(SCN)_3

Cu(en)_2Ag(SCN)_3 crystallizes in space group P2_12_12_1 with its cell parameters, a=7.126(2), b=12.587(5), c=17.585(5). There are four formula units per unit cell(ρ_obs.=1.90g/cm~3, ρ_(calc.=1.96g/cm~3). Diffraction data are collected on a CAD4 four-circle diffractometer using Mo-Ka radiation. The structure is determiued by heavy atom method, then refined by leastsquare method to a final R=0.036. It is shown that in the crystal the coordination of Cu atoms is square pyramidal with four N atoms of en groups in the square plane and oue Natom of thiocyanate group in the apical position. The Ag atom is coordinated tetrahedrally by four S atoms of thiocyanate groups, one of which links up two AgS_4 together, thus forming the infinite AgS_4 tetrahedron chains along a axis.