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.     

Synthesis and Structure of an Interlock Network Frame of Cobalt(Ⅱ) Coordination Polymer {[Co(azpy)_2(NCS)_2]·1/4EtOH·1/2H_2O}_n (azpy=4,4′-Azobispyridine)

A compound {[Co(azpy)_2(NCS)_2]·1/4EtOH·1/2H_2O}_n(1), where azpy=4,4'-azobispyridine, was synthesized and characterized by means of IR, TGA-DTA, magnetic susceptibility and X-ray single crystal diffraction. It consists of two independent sets of fully interlocked two-dimensional networks with the dihedral angle 61.7°, organized in parallel stacks of the sheets which are made of edge-shared [Co(Ⅱ)]_4 squares separated by 0. 9062nm, and defined size rhombic channels. The thermal gravimetric analysis indicates that the framework is stable up to 198℃. The variable-temperature magnetic susceptibility measurements indicated that there is a weak antiferromagnetic interaction between the cobalt(Ⅰ) ions in the complex (1).     

Synthesis,Structure, and the Second-order Nonlinear Optical Properties of a Borate-carboxylic Acid Compound: KB[L-(-)-C4_H_4O_5]_2·H_2O

A new organic-inorganic hybrid noncentrosymmetric potassium bis(malic acid)-borates KB(L-(-)-C_4H_4O_5)_2·H_2O was synthesized by solution method. It was characterized by elemental analysis, FT-IR, TGA and single-crystal X-ray crystallography. It crystallizes in the monoclinic space group P2_(1/c) with a = 5.546(6), b = 11.985(13), c = 9.952(11) ?, β = 97.522(17)°, V = 655.8(13) ?~3, Z = 2, D_c = 1.682 g/cm~3, μ(MoKa) = 0.46 mm~(–1) and F(000) = 340. 5009 reflections were measured and 2893 independent reflections(R_(int) = 0.051) were used for further refinement. Single-crystal X-ray diffraction reveals that the complex exhibits a threedimensional pseudo tunnel structure consisting of fundamental building block [B(L-(-)-C_4H_4O_5)_2]~– anions. The small cavities are occupied by the H_2O molecules, which stabilize the whole structure by O–H×××O hydrogen bonds. The complex exhibits nonlinear optical effect as high as 1.5 times that of KDP standard.     

SYNTHESIS AND CRYSTAL STRUCTURE OF [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2

All attempts to prepare light lanthanide dicyclopeutadienyt chloride failed,due to the disproportionation reaction. The crystal complex of [(η~5-C_5H_5)_2NdCl.OC_4H_8]_2 was successfully prepared by the reaction of NdCl_3·2C_4H_8O with cyclopentadienyl sodium (molar ratio 1:1.8)in tetrahydrofuran at room temperatureThe composition of the title compound was determined by the methods of elemental analysis, infrared spectroscopy and photoelectron spectroscopy. The crystal structure of [(η~5-C_5H_5)_2NdCl·OC_4H_8]_2 was determined from single crystal X-ray diffraction. Data were collected at-60℃ under dry nitrogen atmosphere.The complex crystallizes in the monoclinic space group P2_1/c,with Z=2. Lattice parameters are: a=8.201(3), b=21.589(6),c=8.596(3),β=109.10(3)°.The structure was solved by Patterson and Fourier techniques and refined by least-squares to a final conventional R=0.0636 for 1680 reflections. There are two Nd atoms in the dimeric unit which are bridged asymmetrically by the two chlori     

Synthesis,Structure and Biological Activities of a Novel Anionic Organotin(Ⅳ) Complex {[(pClC_6H_4CH_2)Sn(H_2O)(Cl)_2OCOCH(O)CH(O)CO_2Sn(H_2O)(Cl)_2(p-ClC_6H_4CH_2)]·2(HNEt_3)}

A novel anionic organotin(Ⅳ) complex {[(pClC_6H_4CH_2)Sn(H_2O)(Cl)_2OCOCH(O)CH(O)CO_2Sn(H_2O)(Cl)_2(p-ClC_6H_4CH_2)]·2(HNEt_3)}(1) was synthesized by the reaction of di(p-chlorobenzy)tin dichloride with the D-tartaric acid in 2:1 molar in the presence of an organic base triethylamine. The structure was characterized by elemental analysis, IR, TG, XRD and single-crystal X-ray diffraction. It crystallizes in triclinic, P1 space group, with a = 0.7067(1), b = 1.9762(3), c = 2.2383(3) nm, α = 91.544(2)°, β = 90.075(2)°, γ = 90.110(2)°, V = 3.1247(7) nm~3, Z = 3, Dc = 1.621 g/cm~3, m(Mo Kα) = 16.29 cm–1, F(000) = 1530, R = 0.0394, wR = 0.1092,(Δρ)max = 1224 and(Δρ)min = –840 e/nm~3. The stabilities, orbital energies and composition characteristics of some frontier molecular orbitals of 1 have been carefully investigated with quantum chemistry calculation. In addition, the in vitro antitumor activity suggested that 1 had stronger inhibitory activity on H460, MCF7 than on A549.     

SYNTHESIS AND STRUCTURE OF TWO-ELECTRON HETEROPOLY BLUE K_2H_4SiMo(Ⅴ)_2Mo(Ⅵ)_(10)O_(40)·12H_2O WITH α-KEGGIN STRUCTURE

The single crystal of two-electron heteropoly blue with Si as the heteroatom and α-Keggin structure K_2H_4SiMo(Ⅴ)_2Mo(Ⅵ)_(10)O_(40)·12H_2O was obtained by electrolytic reduction. It crystallizes in a triclinic system with space group P , Mr=2117.73, a= 13.702(4), b=14.107(3), c=14.184(2) ; α=119.27(1), β=93.14(2), ;γ=110. 3(2)°, V=2154.29~3, Z=2, F(000)=1999, μ=36.39cm~(-1), Dc=3.26 g/cm~3. Final R factor is 0.0515. Mo(Ⅴ) is situated in two different edge-shared Mo_3O_(13) groups. The heteropoly blue was characterized by IR, UV, polarography, X-ray photoelectron spectra and ESR. All the results show that the structure of the heteropoly anion with Keggin structure remains unchanged basically in the process of reduction.     

Hydrothermal Synthesis,Structural Characterization and Catalysis Property of a Zr-substituted Polyoxometalate Based on [Zr_2(μ-OH)_2(α-Si W_(11)O_(39))_2]~(10-) Building Blocks

A new Zr-substituted polyoxometalate(POM) [(CH_3)_4N]_6H_2Cs_2(H_2O)_4[Zr_2(μ2-OH)_2(α-SiW_(11)O_(39))_2]·27H_2O(1) was prepared by the reaction of K_(10)[A-α-SiW_9O_(34)]·25H_2O with ZrCl_4 in 0.5 mol/L NaAc-HAc(Ac = CH_3COO~-) buffer solution(pH = 4.5). 1 was characterized by elemental and thermogravimetric analyses, powder X-ray diffraction and single-crystal X-ray diffraction. The title compound crystallizes in monoclinic system, space group P2_(1/m) with a = 13.1865(16), b = 20.964(3), c = 21.432(3) ?, V = 5923.9(12) ?~3, Z = 2, D_c = 3.833 mg/m~3, μ = 22.175 mm~(-1), F(000) = 6116, the final R = 0.0697 and wR = 0.1959 for 10319 observed reflections with I 2σ(I). Single-crystal X-ray structure analysis reveals that 1 exhibits a one-dimensional chain structure based on sandwiched-type POM anions [Zr_2(μ2-OH)_2(α-SiW_(11)O_(39))_2]~(10-) linked by Cs+cations. In addition, catalytic tests indicate that 1 provides a sufficient driving force for the conversion from thioethers to sulfoxides/sulfones by H_2O_2.     

Syntheses and Structures of Two New Cobalt Supramolecular Complexes, [Co(4,4'-bipy)_2(H_2O)_4]· [Co_2(4,4'-bipy)3O(H_2O)_8]·2TST·2(4,4'-bipy)·4H_2 and [Co(4,4'-bipy)_2(H_2O)_4]DSNT'4,4'-bipy

Two new cobalt(Ⅱ) supramolecular complexes [Co(4,4'-bipy)_2(H_2O) _4]·[Co_2(4,4'-bipy)3-(H_2O) _8]·2TST-2(4,4'-bipy)·4H_2O 1 and [Co(4,4'-bipy) _2(H_2O) _4]DSNT·4,4'-bipy 2 based upon the assembly of Co(Ⅱ), 4,4'-bipyridine (4,4'-bipy) and two new multifunctional organic ligands, 2,4,6-tris(4-sulfophenyl-amino)-1,3,5-triazine (H_3TST) and 2,4-bis(p-sulfanilato)-6-diethylamino-1,3,5-triazine (H_2DSNT), have been prepared by hydrothermal method and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal structure of 1 is of monoclinic, space group P2_(1/n) with α= 13.599(4), b = 18.988(6), c = 22.995(7) A, β = 90.273(6)°, V= 5938(3) A~3, Z = 4, C_(56)H_(59)CO_(1.5)N_(13)O_(17)S_3, M_r = 1370.74, D_c = 1.533 g/cm~3,μ = 0.613 mm~(-1), F(000) = 2842, GOOF = 1.018, the final R = 0.0796 and wR = 0.1498 for 9019 observed reflections with I > 2o(I). The crystal structure of 2 belongs to the monoclinic system, space group C2/c with α = 18.864(6), b = 14.283(5), c = 20.246(7) A, β = 107.799(6)°, V = 5194(3) A~3, Z = 4, C_(49)H_(52)CoN_(12)O_(10)S_2, M_r = 1092.08, D_c = 1.397 g/cm~3, μ= 0.480 mm~(-1), F(000) = 2276, GOOF = 1.059, the final R = 0.0665 and wR = 0.1900 for 4887 observed reflections with I> 2σ(I). The results of X-ray crystal structure analysis revealed that complexes 1 and 2 exhibit layered supramolecular frameworks stabilized by electrostatic interactions, π-π interactions and hydrogen bonds.     

Synthesis,Crystal Structure,Thermal Stability,Luminescence and Magnetic Property of a New Mn~Ⅱ Coordination Polymer

One new coordination polymer, [Mn(Hbtc)(bpy)(H_2O)_2]_n 1, was synthesized by the reaction of manganese(Ⅱ) salt under pH-controlled hydrothermal conditions with unsymmetrical polycarboxylic acid of 1,2,4-benzenetricarboxylic acid(H_3btc) and 2,2?-bipyridine(bpy). The structure of complex 1 was characterized by single-crystal X-ray diffraction, IR spectra, powder X-ray analysis, thermal gravimetric analysis(TGA), UV-Vis spectrometry, photoluminescence and magnetic susceptibility. Complex 1 is a one-dimensional(1D) polymeric single-chain structure. Photoluminescence property is quite similar to the bpy ligand. Magnetic susceptibility measurement indicates that 1 shows a weak ferromagnetic coupling between the Mn~Ⅱ ions.     

A Zn(Ⅱ) Coordination Polymer Based on a Flexible Symmetric Multicarboxylate Ligand

A novel coordination polymer, namely [Zn_2(CAPA)(DMA)(H_2O)]_(2n)·n(H_2O)(1,H_4CAPA = 5-(bis(4-carboxybenzyl) amino) isophthalic acid, DMA = N,N-dimethylacetamide) has been synthesized through a solvothermal method and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectra, and thermogravimetric analyses. The crystal structure is of monoclinic, space group P21/n with a = 8.0585(5), b = 18.9733(10), c = 20.2044(14) ?, β = 101.144(7)o, V = 3030.9(3) ?~3, C_(56)H_(54)Zn_4N_4O_(21), M_r = 1378.58, Z = 2). The compound forms a three-dimensional(3D) supramolecular framework by linking adjacent layers via hydrogen bonds and π···π interactions. It is interesting that the crystal structure is much related to the flexibility and configuration of the ligand. In addition, the thermal stability and luminescence properties for the compound have also been investigated.     

Hydrothermal Synthesis,Crystal Structure and Proton Conductivity of a Pr–Ca Heterometal-organic Framework Generated by 1,2,4,5-Benzenetetracarboxylic Acid

A heterometal-organic framework {[Pr_2Ca(betc)_2(H_2O)_7]·H_2O}_n(1) was prepared by the hydrothermal reaction of 1,2,4,5-benzenetetracarboxylic acid(H4betc) with Pr(NO_3)_3 and CaCO_3, and further characterized by single-crystal X-ray structural analysis, elemental analysis, IR, thermal gravimetric, and X-ray powder diffraction. Complex 1 crystallizes in triclinic, space group P1 with a = 7.3668(12), b = 10.1726(14), c = 11.2264(15) ?, a = 100.404(2), b = 106.113(3), g = 109.158(3)o, V = 728.48(19) ?~3, Mr = 966.26, Z = 1, F(000) = 470, Dc = 2.203 g/cm~3, m(Mo Kα) = 3.585 mm~(-1), the final R = 0.0195 and w R = 0.0470(I 2s(I)). Complex 1 is a 3D network with pcu topology with 1D porosity and rich hydrogen-bonding interactions. The proton conductivity of complex 1 was also studied under ~97% relative humidity and the different temperature conditions.     

Synthesis,Crystal Structure and Luminescent Property of a Ag(Ⅰ) Coordination Polymer with a 3D Sandwich-like Framework

A new coordination polymer,{[Ag_2(bpp)_2(H_2O)_2]·bpdc·3H_2O}_n,derived from the ligand biphenyl-4,4'-dicarboxylic acid(H_2bpdc),has been obtained through a hydrothermal technique(bpp = l,3-bis(4-pyridyl)propane).Its single-crystal structure has been characterized by single-crystal X-ray diffraction,powder XRD,FT-IR,TGA and elemental analysis techniques.The single-crystal X-ray diffraction reveals that complex 1 consists of 1D infinite[Ag(bpp)(H_2O)]_n~(n+)cationic chains,2D anionic layer constructed by bpdc anions and free water which provide charge compensation in the crystal structure.The 1D infinite[Ag(bpp)(H_2O)]_n~(n+) cationic chains and 2D anionic layer are further stacked in-ABAB- fashion through intermolecular H-bonding to form a 3D sandwich-like framework.In addition,the luminescent property of complex 1 in the solid state at room temperature was investigated.     

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Novel Water Cluster [Mn(phen)_2·H_2O·Cl]·p-FBA·3H_2O

A novel water cluster [Mn(phen)2·H2O·Cl]·p-FBA·3H2O (p-FBA = p-fluorobenzoic acid and phen = 1,10-phenanthroline) was synthesized by the hydrothermal reaction of MnCl2 with p-FBA and phen at 150 ℃ and characterized by elemental analysis,IR spectra and TG. Its crystal structure was determined by X-ray single-crystal diffraction study. The crystal belongs to the triclinic system,space group P1,with a = 10.5768(1),b = 11.5960(1),c = 12.9916(2) ,α = 101.816(2),β = 95.397(2),γ = 103.052(2)o,V = 1502.8(3) 3,Z = 2,Dc = 1.463 g/cm3,R = 0.0399 and wR = 0.0997. The crystal structure shows that the manganese(Ⅱ ) ion is six-coordinated by four nitrogen atoms,one chloride ion and one oxygen atom forming a distorted octahedral coordination geometry. The structure includes three acyclically connected water molecules and one coordinated water molecule thus forming a (H2O)4 water cluster. This water pattern forms a cross-linked discrete ring. The steady (H2O)4 is further extended into a cage-like structure by the hydrogen-bonding interaction formed by dissociative aqua molecule and Cl-ligand. The dimer structure is further extended into a one-dimensional (1D) structure through C-H···O interaction. π···π Stacking interaction among adjacent phen aromatic rings further stabilizes the crystal structure.     

Hydrothermal Synthesis and Structure of One New Polyoxottmgsate [Ni(trien)]_4[Ni_4(H_2O)_2(HPW_9O_(34))_2]·4H_2O

One new sandwich-type tetra-nickel substituted polyoxotungsate,[Ni(trien)]_4-[Ni_4(H_2O)_2(HPW_9O_(34))_2]·4H_2O(1,trien=triethylenetetramine),has been hydrothermally synthesized and characterized by IR,elemental analysis,TGA,and single-crystal X-ray diffraction analysis.Crystal data for l:triclinic,space group Pī with a=13.279(3),b.13.816(3),C=14.494(4)(A),α=95.403(1),β=113.173(4),γ=93.809(3)°,V=2418.0(10)(A)~3,Z=1 and Dc=3.861g/cm~3.X-ray crystallographic study shows that compound 1 is a relatively rare inorganic-organic hybrid polyoxo tungstate constructed from sandwich Ni-substituted polyoxo-anions and nickel complexes.     

Gear-like array of (H_2O)_(12) as building blocks in one-dimensional supramolecular assembly

The preparation and crystal structure of complex Co(Hsae)_2·2H_2O (1,H_2sae=N-salicylidene-2-iminoethanol) are reported.X- ray analysis revealed that every six Co(Hsae)_2 forms a cyclic chip and every 12 water forms a novel gear-like cluster.Acting as building blocks,the gear-like water cluster and complex chip are connected in A-B fashion and extend into one-dimensional supramolecular chain.Hydrogen bond is the primary bridging force in the formation of supramolecular framework.     

Synthesis,Characterization and Molecular Structure of a Diiron Complex(μ-SCH_2CH_2CH_2S-μ)Fe_2(CO)_5(Ph_2PCH_3)

The title complex,(μ-pdt)Fe_2(CO)_5(Ph_2PCH_3)(pdt = SCH_2CH_2CH_2S),was obtained by the reaction of the parent complex(μ-pdt)Fe_2(CO)_6 with Ph_2PCH_3 and Me_3NO·2H_2O in good yield(90%). The title complex was characterized by IR,~1H NMR,~(31)P{~1H} NMR and ~(13)C{~1H} NMR spectroscopy as well as by single-crystal X-ray diffraction analysis. The molecular structure shows that the title complex contains a butterfly diiron propanedithiolate cluster with five terminal carbonyls and a monophosphine ligand Ph_2PCH_3. The crystal packing diagram reveals that intermolecular C H···O hydrogen bonds between CH_2 and carbonyls,π-π stacking interactions and van der Waals' interactions stabilize the solid state to form a three-dimensional network.     

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.     

CRYSTAL STRUCTURE OF DI(α-HYDROXYISOBUTYRATE)DIAQUO NEODYMIUM NITRATE Nd(C_4H_7O_3)_2NO_32H_2O

The crystal structure of di(-hydroxyisobutyrate)diaquo neodymiumnitrate Nd(C_4H_7O_3)_2NO_32H_2O was determined by X-ray diffraction analysis.It belongs to monoclinic,space group C2/C,with cell dimensionsa=8.996(1),b=8.601(1),c=21.111(3),β=92.38°,V=1632.O,Z=4,D_c=1.83g/cm~3.Crystalstructure has been refined by full-matrix least-square techniques giving afinal R value of 0.036.The neodymium atom is coordinated to eight oxygenatoms.The nitrate group in complex is not bonded to neodymium,each twoneodymium atoms are linked by bridging carboxyl group forming a chainpolymeric molecule.     

Framework Structure of a Synthetic High Silica Zeolite --ZSM-39 from a C_2H_4(OH)_2-H_2O Mixed Solvent System

The structural analogy of clathrate synthesized with natural zeolite framework is well known. HPF_6·6H_2O and (CH_3)_4 (OH)·5H_2O are isostructural with sodalite,melanophlogite is isostructural with the 12 cubic gas hydrate and zeolite ZSM-39 with the 17 gas hydrate. The synthesis of ZSM-39 was first reported by Brace in 1981.Schleker and Meier also obtained the crystals of ZSM-39 with size<10μm and analyzed its crystal stucture by the powder X-ray diffraction.In 1984,Gies solved the crystal structure of dodecasil 3C(ZSM-39) synthesized from an aqueous system in space group F_(ds).In the present paper,we report the framework structure of the high silica zeolite—ZSM-39 obtained from the ethylene glycol-water mixed solvent system.     

One Novel 2D Co(Ⅱ) Polymer with 1,2,3-Triazole Derivative: Crystal Structure,Fluorescence and Hirshfeld Surface Analysis

One new polymer [Co(L)(H_2O)_2]_n(1) was synthesized by 4-(ethoxycarbonyl)-5-methyl-1H-1,2,3-triazole-1-carboxylic acid(Emtc) under the in situ solvent thermal reaction(H_2L = 1-(carboxymethyl)-5-methyl-1H-1,2,3-triazole-4-carboxylic acid). The title complex performs a wave-like 2D framework and the ligand H_2L demonstrates the coordination mode as μ4-η~2:η~1η~1:η~1. The crystal structure has been established by single-crystal X-ray diffraction, and characterized by FT-IR. Fluorescent property was investigated in this work. Hirshfeld surface analysis has also been carried out on 1, and obvious main intermolecular interactions are observed.