A New Mn(Ⅱ) Coordination Polymer with a Rare Polyrataxane Topology: Synthesis,Crystal Structure and Luminescent Property

A novel coordination polymer [Mn(bcp)(bib)0.5]n(1, H2 bcp = 1,3-bis(4-carboxyphenoxy)propane and bib = 1,4-bis(imidazol-1-yl)benzene) was synthesized under hydrothermal conditions, and was characterized by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy and powder X-ray diffraction(PXRD).Complex [Mn(bcp)(bib)0.5]n(1) is of triclinic system, space group P1 with a = 7.320(5), b =11.871(5), c = 13.932(5) ?, α = 111.125(5)°, β = 99.658(5)°, γ = 101.104(5)°, Z = 2, V= 1070.3(9)?3 Mr = 474.34, Dc = 1.472 g/cm3, F(000) = 488, μ = 0.660 mm?1, the final R = 0.0353 and wR =0.0.984 for 4373 observed reflections with I 2?(I). Structure analysis reveals that complex 1 displays a rare 2 D + 2 D → 2 D polyrataxane topology. Moreover, the luminescent property for 1 was investigated at room temperature.     

Synthesis,Crystal Structure and Theoretical Calculations of a Cadmium Complex Containing 3-Hydroxybenzoic Acid and 1,4-Bis(imidazol-1-yl)-butane

A new complex [Cd(hba)_2(bib)]n·nH_2O(1,Hhba = 3-hydroxybenzoic acid,bib = 1,4-bis(imidazol-1-yl)-butane) has been hydrothermally synthesized and characterized by elemental analysis,IR spectrum,thermogravimetric analysis,fluorescence spectrum,and singlecrystal X-ray diffraction.Yellow crystal crystallizes in the orthorhombic system,space group Pbca with a = 16.220(5),b = 14.980(5),c = 20.521(5) ?,V = 4986(3) ?~3,C_(24)H_(26)CdN_4O_7,Mr = 594.89,Dc = 1.585 g/cm~3,μ(Mo Kα) = 0.927 mm~(-1),F(000) = 2416,Z = 8,the final R = 0.0242 and w R = 0.0589 for 4076 observed reflections(I 2s(I)).In 1,the Cd(Ⅱ) ion takes a six-coordination mode,and bib ligand bridges adjacent Cd(Ⅱ) ions to generate 1D zigzag chains; these neighboring chains are connected by O–H···O hydrogen bonding interactions,producing a 2D folded layered structure.Furthermore,by O–H···O hydrogen bonding between layers and layers,a 3D supramolecular architecture is formed.In addition,we analyzed Natural Bond Orbital(NBO) in using the PBE0/LANL2 DZ method built in Gaussian 03 Program.The calculation results indicated obvious covalent interaction between the coordinated atoms and Cd(Ⅱ) ion.     

Catalytic Kinetic on the Thermal Decomposition of Ammonium Perchlorate with a New Energetic Complex Based on 3,5-Bis(3-pyridyl)-1H-1,2,4-triazole

A new energetic complex,[Co(3,3?-Hbpt)(Htm)]·H_2O(1,3,3?-Hbpt = 3,5-bis(3-pyridyl)-1H-1,2,4-triazole and H_3tm = trimesic acid),has been synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction,elementary analysis,IR spectroscopy,thermogravimetric analysis and X-ray powder diffraction. Single-crystal X-ray diffraction indicates that the complex belongs to triclinic system,space group P 1 with a = 10.0911(1),b = 10.2573(1),c = 10.6393(1) ?,α = 103.793(2),β = 101.041(2),γ = 107.918(3)o,V = 974.9(2) ?~3,Z = 2,D_c = 1.732 g·cm-3,μ = 0.941 mm~(-1),M_r = 508.31,F(000) = 518,the final R = 0.0523 and wR = 0.0935 with I 2σ(I). In the title complex,Co(Ⅱ) ions are connected by Htm2-anions generating 1D ladder-like chains which are linked by 3,3?-Hbpt to form 1D cages. In addition,the thermal decomposition of ammonium perchlorate(AP) with complex 1 was explored by differential scanning calorimetry(DSC). AP is completely decomposed in a shorter time in the presence of complex 1,and the decomposition heat of the mixture is 2.531 kJ·g~(-1),significantly higher than that of pure AP. By Kissinger's method,the ratio of Ea/ln(A) is 11.05 for the mixture,which indicates that complex 1 shows good catalytic activity toward the AP decomposition.     

A New Nickel(Ⅱ) Coordination Compound Constructed by Pyridyl-triazole and Oxybis(Benzoic Acid): Synthesis,Crystal Structure and the Effect on the Thermal Decomposition of Ammonium Perchlorate

A new energetic complex, Ni(3,4'-Hbpt)2(Hoba)2(H2O)2(3,4'-Hbpt = 3-(3-pyridyl)-5-(4'-pyridyl)-1-H-1,2,4-triazole and H2 oba = 4,4'-oxybis(benzoic acid)), has been synthesized by hydrothermal reaction and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, thermogravimetric analyses and X-ray powder diffraction. Single-crystal X-ray diffraction analysis indicates that the complex belongs to the monoclinic system, space group P21/c with a = 10.2357(9), b = 24.594(2), c = 10.4225(9) A, β = 114.0110(10)°, V = 2396.7(4) A3, Dc =1.460 g/cm3, μ = 0.482 mm-1, Mr = 1053.63, F(000) = 1088, Z = 2, the final R = 0.0358 and wR =0.0973 with I 2σ(I). Both 3,4'-Hbpt and H2 oba ligands adopt monodentate modes linking one Ni(II)ion to form a 0D motif. Furthermore, the 0D motifs are linked into a 3D supramolecular architecture with hydrogen bonds. In addition, the catalytic performance for thermal decomposition of the efficacy of ammonium perchlorate(AP) is explored by differential scanning calorimetry(DSC),which indicates that the complex is a good candidate for a promoter of the thermal decomposition of ammonium perchlorate.     

Solvothermal Synthesis and Crystal structure of a Two-dimensional Cd（Ⅱ） Complex Based on a Flexible Carboxylate Ligand

A two-dimensional Cd(II) coordination polymer, [Cd(dtb)]n (dtb=5,5-dithiobis(2- nitrobenzoic acid), has been solvothermally synthesized and characterized by elemental analysis, IR, TG analysis and single-crystal X-ray diffraction analysis. The complex crystallizes in the monoclinic P21/c space group, with a=10.7147(10), b=7.4518(7), c=22.053(2), β=95.477(2)o, V=1752.7(3)3, Z=4, Mr=524.74, Dc=1.989 g/cm3 and F(000)=1032. The final R=0.0453 and wR=0.1201 for 2950 observed reflections with I>2σ(I). In the complex, the Cd(II) ion is coordinated with six oxygen atoms from four different carboxylate groups of dtb ligands and one lattice water molecule. The adjacent Cd centers are interconnected by the flexible carboxylate ligand to form a two-dimensional (2D) structure.     

Hydrothermal Synthesis,Crystal structure,DFT and Application of a Dinuclear Cadmium(Ⅱ) Complex Based on NPHSNPAB

A new dinuclear cadmium(Ⅱ) complex,[Cd(NPHSNPAB)(H_2O)_2(CH_3CH_2OH)]_2(1),was synthesized by the hydrothermal reaction of N-phenyl-2-[2-hydroxyl-3-sulfo-5-nitrophenylazo]butadiene-1,3(NPHSNPAB) and Cd(NO_3)_2·4H_2O,and characterized by elemental analysis,infrared,UV-visible,fluorescence,thermal behavior and single-crystal X-ray diffraction. For this complex: C_(36)H_(42)Cd_2N_8O_(22)S_2,Mr = 1227.74,triclinic system,space group P1,a = 7.555(9),b = 12.006(14),c = 13.943(16) ?,α = 67.955(2),β = 88.573(2),γ = 77.550(2)o,V = 1142.5(2) ?~3,Z = 2,Dc = 1.784 g/cm~3,λ = 0.71073 ?,F(000) = 620,S = 1.125,R = 0.0460 and w R = 0.1159 for 3949 observed reflections with I 2(I). X-ray diffraction analysis reveals that the central Cd(Ⅱ) ion is bound by six oxygen atoms,forming a slightly distorted octahedral geometry. Density functional theory of complex 1 was studied. Noticeably,the application of 1 on metallic yarn got good effect.     

Synthesis,Structures, and Fluorescence Property of a Novel Heterometallic Complex Constructed by Imidazole

A novel heterometallic complex constructed by imidazole ligand, CoZn(C_3N_2H_3)_4(1), has been synthesized under hydrothermal conditions. Compound 1 was characterized by IR spectra, thermal analysis, powder X-ray diffraction and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies reveals that compound 1 is in the tetragonal system, space group I4_1cd with a = 23.4371(5), b = 23.4371(5), c = 12.4430(7) ?, V = 6834.9(4) ?~3, Z = 16, C_(12)H_(12)CoN_8Zn, M_r = 392.60, D_c = 1.526 g/cm~3, F(000) = 3152, μ = 2.381 mm~(–1), R = 0.0323 and w R = 0.0789. The CoZn(C_3N_2H_3)_4 is one-dimensional heterometallic molecular chains, which are further extended into a 3D open framework. Moreover, the solid-state fluorescence property of the complex has also been investigated at room temperature.     

Synthesis,Crystal Structure,Fluorescent Property and DFT Calculations of a New Zn(Ⅱ) Complex Based on 3-(2-Pyridyl)-5-(4-pyridyl)-1H-1,2,4-triazole

A new coordination compound Zn(2,4?-bpt)2(H_2O)(1) based on the versatile ligand 2,4?-Hbpt(2,4?-Hbpt = 3-(2-pyridyl)-5-(4-pyridyl)-1H-1,2,4-triazole) was prepared by hydrothermal reactions. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis indicates that the complex belongs to monoclinic system, space group C2/c with a = 23.877(3), b = 0.7483(9), c = 1.2492(2) ?, b = 92.681(2)°, V = 2230.6(4) ?3, Z = 4, Dc = 1.572 g/cm~3, m = 1.143 mm~(-1), Mr = 527.85 and F(000) = 1080. The final R = 0.0581 and w R = 0.0898 with I 2s(I). 1 is a 0D motif which is connected by hydrogen bonds to form a corrugated 1D pattern. In addition, 1 shows strong photoluminescent emissions in the solid state at room temperature which can be used as potential optical materials. Theoretical calculations based on density functional theory(DFT) were employed in order to explicate the stability and chemical reactivity of 2,4?-Hbpt with different conformations. The results indicated that conformation I is more stable and prior to coordination in the reactions.     

Synthesis, Crystal Structure and Properties of a Novel Vanadium（Ⅴ） Oxoperoxo Complex Incorporating a Tridentate Hydrazone Ligand

A novel vanadium(V) oxoperoxo complex [VOO2(APTCH)(CH3OH)] (HAPTCH = 2-acetylpyridine thiophene-2-carboxylic hydrazone) has been synthesized and characterized by IR, TGA and X-ray single-crystal structure determination. The complex crystallizes in the monoclinic system, space group P21/c with a = 11.232(2), b = 10.762(2), c = 112.613(3), β = 99.44(3)°, V = 1504.1(5)3, Dc = 1.657 g·cm-3, Z = 4, F(000) = 768, μ = 0.827 mm-1, the final R = 0.0392 and wR = 0.1073 for 2266 observed reflections with I > 2σ(I). Single-crystal X-ray diffraction studies reveal that the vanadium(V) is coordinated by a tridentate ligand, methanol molecule and peroxo group to form a pentagonal-bipyramidal geometry. The crystal structure is stabilized by intermolecular hydrogen bonds of O-H···N and C-H···O.     

Hydrothermal Synthesis,Crystal Structure and Fluorescent Property of a Cd(Ⅱ) Complex Based on Biimidazole and Isonicotinate-N-oxide

A new complex [Cd(H2biim)2(H2O)2]·(ino)2·4H2O (H2biim = 2,2'-biimidazole, ino = isonicotinate-N-oxide) has been prepared and characterized by single-crystal X-ray diffraction analysis, IR and fluorescence spectra analysis. The crystal is of triclinic system, space group P1 with a = 7.5380(6), b = 8.0402(7), c = 13.5094(11) , α = 104.269(1), β = 93.604(1), γ = 98.349(1)°, V = 780.93(11) 3, Mr = 765.00, Dc = 1.627 g/cm3, F(000) = 390, μ = 0.776 mm-1 and Z = 1. The final R = 0.0322 and wR = 0.0825 for 7038 observed reflections with I 2σ(I) and R = 0.0341 and wR = 0.0832 for all data. The title complex exhibits an infinite chain-like structure through bridging isonicotinate-N-oxide. Strong interchain hydrogen bonds between isonicotinate-N-oxide and H2biim result in the robust 3-D supramolecular architecture. Moreover, the complex shows strong photoluminescence with emission maximum at λ = 401 nm upon λex = 330 nm.     

Synthesis,Crystal Structure and Catalytic Activity of a Pd-PEPPSI Complex Bearing Bromine Group

A new Pd-PEPPSI complex(2) with the bromo groups on the para-positions of N-aryl moieties of NHC has been synthesized and characterized by NMR and X-ray single-crystal diffraction. Complex 2 crystallizes in monoclinic, space group P2_1/c with a = 11.8790(8), b = 14.3038(10), c = 15.9905(11) ?, β = 101.291(2)°, V = 2664.4(3) ?3, Z = 4, D_c = 1.722 Mg/m~3, μ = 3.913 mm~(-1), F(000) = 1352, the final R = 0.0682 and wR = 0.1914 for 15113 observed reflections(I 2σ(I)), R(all data) = 0.0970, w R(all data) = 0.2115, completeness to theta of 25.00 is 100.0% and GOOF = 1.035. Influenced by the electron-withdrawing bromo groups, the Pd-PEPPSI complex(2) showed high catalytic activity for the Suzuki-Miyaura cross-coupling reactions of aryl chlorides and arylboronic acids with a low catalyst loading(0.05 mol%) at room temperature in air.     

An Imidazole-functionalized Dioxovanadium Complex with the Highly Selective Oxidation of Sulfides

A novel imidazole-functionalized dioxovanadium complex [V_2O_2(C_2O_4)(aIM)_4](aIM = 1-allylimidazole) was synthesized by the reaction of VO(acac)_2 with 1-allylimidazole and fully characterized by single-crystal X-ray diffraction(SCXRD),powder X-ray diffraction(PXRD),X-ray photoelectron spectroscopy(XPS),Fourier transform infrared spectroscopy(FT-IR) and elemental analyses. Interestingly,the oxalate was in-situ generated from the acetylacetone anion of VO(acac)_2 and further coordinated with the vanadium cation and finally complex 1 was achieved. The crystal of complex 1 belongs to the monoclinic system,space group P2_1/n with a = 10.7922(9),b = 10.6296(8),c = 13.2936(11) ?,μ = 0.677 mm~(-1),M_r = 686.48,V = 1516.9(2) ?~3,Z = 2,D_c = 1.503 g/cm~3,F(000) = 708,R = 0.0543,and wR = 0.1517 for 2459 observed reflections with I 2σ(I). Notably,complex 1 is further used as catalyst in the oxidation of sulfides using H_2O_2 as the oxidant and exhibits excellent catalytic performance(conv. up to 95.6%,sele. up to 98.9%).     

CRYSTAL AND MOLECULAR STRUCTURE OF BENZO-15-CROWN-5 POTASSIUM TETRACHLOROAURATE K(C_(14)H_(20)O_5)_2-AuCl_4

<正> The crystal and molecular structure of the title compound K(C14 H20O5)2AuCl4 has been determined by X-ray diffraction method.The crystallographic data are as follows;Mr=914.51,triclinic,space group P1,a=10.988(2),b=13.472(4),c=13.696(2)A,α=77.72(1),β=79.02(2),γ=64.92(2)°,V=1782.6(4)A3,Z=2,Dc=1.704 g.cm-3,μ=45.858 cm-1,F(000)=454,R=0.019,Rw=0.018 for 5697 observed reflections with I≥3σ(I).X-ray structure determination shows that benzo-15-crown-5(B15C5)forms a 2:1 complex with KAu-C14 in which K+is sandwiched between two crown rings.The dihedral angle between these two ether oxygen planes is 11.9°.The anion AuCl4-has a planar square configuration which is bound with the complex cation K(B15C5)2+by electrostatic force to form an ion-pair.     

Cadmium（Ⅱ） Nitrite Complex Based on the Bis（2-benzimidazole） and Aromatic Carboxylate Ligands

A new cadmium(Ⅱ) nitrite complex Cd2(H2C3PIm)2(BDC)(NO2)2(1,H2C3PIm = 2,2'-(1,3-propanediyl)bis(1H-benzimidazole),H2BDC = 1,4-benzenedicarboxylic acid) has been synthesized by solvothermal reaction in formamide,and its structure(C42H36Cd2N10O8,Mr = 1033.61) was determined by single-crystal X-ray diffraction analysis.The crystal belongs to the monoclinic system,space group P21/n with a = 0.9859(5),b = 0.8936(5),c = 2.3188(5) nm,β = 97.576(5)°,V = 2.025(16) nm3,Z = 2,Dc = 1.695 g/cm3,μ(MoKα) = 1.118 mm-1,F(000) = 1036,S = 1.017,the final R = 0.0304 and wR = 0.0752 for 3761 reflections with I > 2σ(I).The centrosymmetric complex 1 contains a dimer in which two distorted octahedral Cd(II) centers are bridged by BDC ligand and chelated by H2C3PIm.The units of the complex are linked via weak N-H···O hydrogen bonds between the nitrito and the BDC ligands,leading to the formation of a 1D zigzag chain along the b axis.The π-π packing interactions contribute to the formation of a three-dimensional supramolecular architecture.The complex exhibits strong photoluminescence at room temperature.     

Synthesis and Crystal Structure of a New Zinc(Ⅱ) Coordination Polymer Assembled by 4-Nitrophthalic Acid and Bis(imidazol) Ligands

A new complex [Zn(4-nph)(bib)]_(2n)·nH_2O(1) has been obtained by the reaction of metal(Zn(Ⅱ)),1,4-bis(imidazol-1-yl)-butane(bib) with 4-nitrophthalic acid(4-H_(2nph)).The crystal structure of 1 has been determined by single-crystal X-ray diffraction analysis.Compound 1 is of triclinic system,space group P1 with a = 10.3251,b = 12.4503,c = 16.6497 ?,α = 88.487(3),β = 72.529(3),γ = 79.991(3)°,V = 2009.8(5) ?~3 and Mr = 945.47.Complex 1 shows a three-dimensional(3 D) framework.Moreover,through intermolecular hydrogen bonds,compound 1 is assembled into a supramolecular structure.The thermal stability and luminescent properties of 1 are also investigated.     

A Three-dimensional Cd(Ⅱ) Coordination Polymer with Unique 8-Connected LOMFOI Topology Based on Mixed Flexible N/O Ligands

A new metal-organic framework,{[Cd(DPA)(OBA)]·(H2O)}n(1,DPA = 4,4-dipyridylamine,H2OBA = 4,4-oxybisbenzoic acid),has been synthesized and characterized by elemental analysis,IR and single-crystal X-ray diffraction.Single-crystal X-ray analysis shows that it is a 3-D framework.Complex 1 crystallizes in monoclinic,space group C2/c with a = 21.699(7),b = 12.192(4),c = 17.566(5) ,β = 105.254(5)°,V = 4483.43 3,Z = 8,Dc = 1.653 g/cm3,μ = 1.021 mm-1,F(000) = 2240,the final R = 0.0307,wR = 0.0867(I 2σ(I)).Complex 1 exhibits a rare three-dimensional highly 8-connected LOMFOI topology with a point symbol of {424·64}.Thermogravimetric analysis shows that the decomposition temperature of the host framework of the complex is above 400 ℃.     

Crystal Structure and Inhibitory Activity against Xanthine Oxidase of Bis(μ_2-chloro)-chloro-(μ-N,N'-(2-pyridylmethylene) Furanmethanoamine Copper(II) Complex

A chloro-bridged dinuclear copper(II) complex with ligand 2-pyridylme-thylene-furfurylamine has been synthesized and characterized by single-crystal X-ray diffraction, and its inhibitory activity on xanthine oxidase (XO) was also evaluated. It crystallizes in the triclinic system, space group P1 with a=8.0441(16), b=8.5663(17), c=10.060(2), α=77.52(3), β= 72.04(3), γ=70.12(3)°, V=615.3(2)3, Z=1, Dc=1.731 g/cm3, F(000)=322, the final R= 0.0401 and wR=0.0934 for 1971 observed reflections with I > 2σ(I). X-ray analysis reveals that the Cu(II) cation is five-coordinated by two N atoms of Schiff base and three Cl anions. The C-H…Cl intermolecular and intramolecular hydrogen bonds connect the molecules to form a three-dimensional network. This copper(II) complex shows more potent inhibitory activity against XO with IC50=3.48 μM than the standard inhibitor allopurinol.     

Synthesis,Crystal Structure and Catalytic Properties of a New 2D Nickel(II) Coordination Polymer Based on Flexible Bis(benzimidazole)

A new Ni(II) coordination polymer [Ni(L)2(SCN)2]n(L = 1,4-bis(benzimidazol-1-yl)butane) was synthesized hydrothermally and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group C2/c with a = 9.4760(3), b = 24.0408(8), c = 16.5871(5) A, β = 99.832(3)°, V = 3723.2(2) A3, Z = 4, Dc = 1.348 g/cm3, F(000) = 1576, the final R = 0.0486 and w R = 0.0936 for 2938 observed reflections with I 2σ(I) for the complex. Structural analysis shows that the coordination polymer possesses a 2D(4,4) layer structure which is composed of Ni(II) centers bridged by L ligand with two kinds of conformations and further assembled into a 3D supramolecular network via π-π stacking interactions. In addition, the fluorescence and catalytic properties, for the degradation of Congo red, of the complex were investigated.     

Hydrothermal Synthesis,Crystal Structure and Thermal Stability Properties of the Complex [Cd_2(phen)_2(C_(14)H_(11)O_3)_4(CH_3CH_2OH)]·(CH_3OH)·(H_2O)

A dinuclear cadmium complex [Cd2(phen)2(C14H11O3)4(CH3CH2OH)]·(CH3OH)·(H2O) has been synthesized with benzilic acid and 1,10-phenanthroline by hydrothermal method.The crystal structure was determined by X-ray diffraction with crystal parameters as follows:triclinic system with space group P1,a = 1.21298(10),b = 1.32586(11),c = 2.4815(2) nm,α = 76.2630(10),β = 81.4500(10),γ = 69.1700(10)o,V = 3.6143(5) nm3,Dc = 1.438 g/cm3,Z = 1,F(000) = 1600,the final GOOF = 0.937,R = 0.0521 and wR = 0.1328.In the title complex,the dinuclear structure is defined by carboxyl oxygen atoms adopting a monodentate bridged coordination mode.The coordination environment of Cd(Ⅱ) ion is CdO4N2,giving a distorted octahedral coordination geometry.TG analysis shows that the title complex is stable under 140 ℃.     

A Novel Three-dimensional Triazole-based Zinc(Ⅱ) Coordination Polymer Controlled by the Spacers of Dicarboxylate Ligand with(4~2,6~2,8~2)(4,6~2,8~3) Topology

A novel mixed-ligand coordination polymer [Zn(BTA)(ip)0.5]n(1, HBTA = benzotriazole, H2 ip = isophthalic acid) has been synthesized under hydrothermal conditions, which was further characterized by X-ray diffraction, IR spectrum, elemental analysis and TG-DTA experiments. Complex 1 crystallizes in monoclinic system, space group Pnma with a = 8.9731(5), b = 22.0477(12), c = 10.0217(5) ?, V = 1982.66(18) ?3, Z = 8, C10 H6 ZnN3 O2, Mr = 265.55, Dc = 1.779 g/cm3, μ = 2.462 mm-1, F(000) = 1064, the final R = 0.0225 and wR = 0.0652 with I 2?(I). This complex is a 3 D framework with the(42,62,82)(4,62,83) topology. Furthermore, the thermal stability of complex 1 is observed to be dependent on the polymeric structure nature. Strong solid-state luminescence emissions suggest that complex 1 is a good candidate for light emission materials.