Synthesis,Structure and Acaricidal Activity of Tricyclohexyltin Benzoate

Tricyclohexyltin 4-amino-3-methyl-benzoate(1) and tricyclohexyltin 3,4-dimethoxybenzoate(2) were synthesized and their crystal structures were determined by X-ray diffraction. Compound 1 belongs to the monoclinic system, space group P21/c with a = 14.0554(15), b = 11.6947(13), c = 16.2720(17) , Z = 4, V = 2565.7(5) 3, Dc = 1.341 g·cm-3, μ(MoKα) = 1.016 mm-1, F(000) = 1080, R = 0.0833 and wR = 0.2964. Compound 2 is of monoclinic system, space group C2/c with a = 17.8712(6), b = 8.4433(3), c = 35.5783(13) , Z = 8, V = 5366.8(3) 3, Dc = 1.360 g·cm-3, μ(MoKα) = 0.980 mm-1, F(000) = 2288, R = 0.0549, wR = 0.1279. In compounds 1 and 2, the central Sn atom is coordinated in a tetradentate manner to assume a distorted tetrahedral configuration. Preliminary biological tests showed that these two compounds have strong acaricidal activity.     

Construction and Photoluminescence Properties of Zn(Ⅱ)/Cd(Ⅱ) Complexes with 4-Amino-3,5-propyl-1,2,4-triazole Ligand

Reaction of ZnCl2 and 4-amino-3,5-propyl-1,2,4-triazole(dpatrz) or CdCl2, NaN3 and dpatrz, in aqueous solution at room temperature yields two neutral clusters: a dinuclear complex [Zn2(dpatrz)2Cl4](I) and a linear trinuclear complex, [Cd3(dpatrz)4(N3)2Cl4](Ⅱ). Both complexes have been characterized by X-ray single-crystal diffraction, powder XRD, IR, elemental analysis, TG and fluorescence analysis. Complex I crystallizes in orthorhombic, space group Pbca with a = 11.865(2), b = 14.464(3), c = 15.985(3) , V = 2743.4(9) 3, Z = 4, C16H32N8Cl4Zn2, Mr = 609.4, Dc = 1.475 g·cm3, μ = 2.16 mm-1, F(000) = 1248, GOOF = 1.091, the final R = 0.0295 and wR = 0.0665 for 1999 observed reflections(I 2σ(I)). Complex Ⅱ crystallizes in monoclinic, space group P21/c with a = 11.408(2), b = 15.211(3), c = 18.152(6) , β = 123.75(2)o, V = 2619.1(1) 3, Z = 2, C32H64N22Cl4Cd3, Mr = 1236.05, Dc = 1.567 g·cm3, μ = 1.46 mm-1, F(000) = 1244, GOOF = 1.042, the final R = 0.0444 and wR = 0.0913 for 3466 observed reflections(I 2σ(I)). The analysis of X-ray revealed that both structures lie about the inversion centers: complex I adopts two μ1,2-triazole bridges linking two Zn(Ⅱ) ions and Ⅱ forms a linear trinuclear structure with four μ1,2-triazoles and two μ1,1-N3- bridging modes. There are different coordinated geometries for three Cd(Ⅱ) ions in Ⅱ: one is coordinated with an octahedral environment, and the other two are distorted tetragonal pyramids(τ = 0.34). The hydrogen bonds of C–H···Cl and N–H···Cl lead to the discretes into a 3D supramolecular network in both compounds. The thermal stabilities and photoluminescence behaviors of them were also studied.     

Two Cobalt(II) Complexes Derived from the Hydrolysis Product of Di-Schiff Base Ligand N,N'-Bis-(1-benzimidazo-2-yl-ethylidene)-ethane-1,2-diamine:Preparation,Characterization and Crystal Structure of the 6-Coordinate Species [CoL_2]X·H_2O (X = ClO_4~-, NO_3~-)

The reactions of Co(ClO4)2·6H2O and Co(NO3)2·6H2O with the di-Schiff base ligand N,N'-bis-(1-benzimidazo-2-yl-ethylidene)-ethane-1,2-diamine (LA) in ethanol have been investigated. The reactions of LA with excess amount of cobalt salts yield the six-coordinate complexes [CoL2](ClO4)2·H2O 1 and [CoL2](NO3)2·H2O 2 as isolatable products (L = N-(1-benzimidazo-2-yl-ethylidene)-ethane-1,2-diamine), where L is a tri-dentate mono-Schiff base ligand, resulting from the hydrolysis of the precursor di-Schiff base LA. Both complexes were characterized by X-ray crystallography. Crystal data for complex 1: monoclinic, space group P21/c, a = 11.9214(10), b = 23.5828(17), c = 14.0387(12) , β = 135.219(4)o, C22H30Cl2CoN8O9, Mr = 680.37, V = 2780.1(4) 3, Z = 4, Dc = 1.625 g/cm3, μ(MoKα) = 0.876 mm-1, F(000) = 1404, the final R = 0.0725 and wR = 0.1530 for 5726 observed reflections (I > 2σ(I)). Crystal data for complex 2: monoclinic, space group P21/c, a = 18.2162(16), b = 10.0610(6), c = 18.593(2) , β = 130.099(3)o, C22H30CoN10O7, Mr = 605.49, V = 2606.5(4) 3, Z = 4, Dc = 1.543 g/cm3, μ(MoKα) = 0.722 mm-1, F(000) = 1260, the final R = 0.0619 and wR = 0.1429 for 5194 observed reflections (I > 2σ(I)). X-ray diffraction analysis reveals that each cobalt atom in the two complexes is chelated by six nitrogen atoms from two tridentate ligands L, exhibiting a slightly distorted octahedral coordination sphere. In both complexes, the strong hydrogen-bonding interactions between the lattice waters and N-H groups of the ligands result in 1D chains which are further connected by ClO4-(or NO3-) groups to form a 3D framework. In complex 2, the strong π-π interactions increase the stability of the structure.     

Syntheses and Structure Determination of Two Copper Compounds with 4,4--Sulfonyldibenzoilate Ligands

The two title compounds [Cu(sdba)(py)2(H2O)]n·2n(py) 1 and [Cu(sdba)(phen)(H2O)]n 2(H2sdba = 4,4'-sulfonyldibenzoic acid,py = pyridine,phen = 1,10-phenanthroline) have been synthesized and characterized by single-crystal structure determination,IR and TG analyses.Compound 1 crystallizes in orthorhombic,space group Pbcm with a = 5.9833(12),b = 22.333(5),c = 24.571(5),V = 3283.3(12) 3,Z = 4,C34H30N4O7SCu,Mr = 702.22,Dc = 1.388 g/cm3,F(000) = 1396,μ(MoKα) = 0.780 mm-1,the final R = 0.0599 and wR = 0.1767 for 3416 observed reflections with I > 2σ(I).Compound 2 crystallizes in monoclinic,space group C2/c with a = 22.9549(4),b = 12.2443(3),c = 17.8687(4) ,β = 110.873(1)°,V = 4692.69(18) 3,Z = 8,C26H18N2O7SCu,Mr = 566.02,Dc = 1.602 g/cm3,F(000) = 2312,μ(MoKα) = 1.078 mm-1,the final R = 0.0697 and wR = 0.1330 for 3452 observed reflections with I > 2σ(I).In both structures,the CuII metal centers adopt five-coordination in slightly distorted tetragonal pyramidal geometries,while the second N-donor ligands bond or chelate to CuII ions as the terminal moiety.The weak interactions extend the two structures into high-dimensional supramolecular coordination-polymers.     

[N-ethyl-4,4'-bipyridinium][ZnX_4](X = Cl or Br) with N-ethyl-4,4'-bipyridinium Generated In Situ:Syntheses,Structures, Fluorescence and TDDFT Calculations

Two new zinc bipyridinium compounds, [N-ethyl-4,4′-bipyridinium][ZnX4](X = Cl(1) or Br(2)) with N-ethyl-4,4′-bipyridinium generated in situ, have been synthesized through solvothermal reactions and structurally characterized by single-crystal X-ray diffraction analyses. Both compounds are isostructural and crystallize in the P21/c space group of monoclinic system. Compound 1: a = 8.4397(5), b = 21.988(1), c = 8.8777(5) , β = 106.490(1)°, V = 1579.7(2) 3, C12H15Cl4N2 Zn, Mr = 394.43, Z = 4, Dc = 1.658 g/cm3, S = 1.068, μ(MoKα) = 2.218 mm-1, F(000) = 796, R = 0.0295 and wR = 0.0766. Compound 2: a = 8.4154(6), b = 22.844(2), c = 9.0308(7) , β = 106.026(1)°, V = 1668.6(2) 3, C12H15Br4N2 Zn, Mr = 572.27, Z = 4, Dc = 2.278 g/cm3, S = 1.033, μ(MoKα) = 11.038 mm-1, F(000) = 1084, R = 0.0427 and wR = 0.1175. Both of them are characteristic of an isolated structure with the zinc atoms locating at a tetrahedral environment. In both compounds, the N-ethyl-4,4′-bipyridinium2+ cations and ZnX42– anions interconnect together via hydrogen bonding interactions to construct a three-dimensional(3-D) supramolecular framework. Fluorescent studies reveal that both compounds exhibit a strong emission in the green region. In combination with the theoretical calculations, we can draw a conclusion that the emissions should result from ligand-toligand charge-transfer(LLCT) transition.     

Syntheses, Crystal Structures and Magnetism of Two New Coordination Polymers [Ni（bix）2Cl2]n and [Co（bix）Cl2]n

The self-assembly reactions of MIICl2 (M = Ni, Co) with the flexible bix ligand [bix = 1,4-bis(imidazole-1-ylmethyl)benzene] yielded a 2D network [NiII(bix)2Cl2]n 1 and a 1D chain [CoII(bix)Cl2]n 2. Their crystal structures have been determined by X-ray single-crystal diffraction analysis. Complex 1 characters a two-dimensional grid-type structure and crystallizes in monoclinic, space group P21/c with a = 7.7231(7), b = 12.7787(9), c = 13.9374(13) , β = 105.419(4)o, C28H28Cl2N8Ni, Mr = 606.19, Ζ = 2, V = 1326.0(2) 3, Dc = 1.518 g/cm3, μ = 0.969 mm-1, F(000) = 628, R = 0.0429 and wR = 0.0783 for 2503 observed reflections (I > 2σ(I)). Compound 2 is a one-dimensional chain and crystallizes in orthorhombic, space group Pbca with a = 11.3696(6), b = 10.2128(6), c = 14.4943(9) , C14H14Cl2CoN4, Mr = 368.12, Z = 4, V = 1683.01(17) 3, Dc = 1.453 g/cm3, μ = 1.334 mm-1, F(000) = 748, R = 0.0317 and wR = 0.0800 for 1778 observed reflections (I > 2σ(I)). Magnetic properties of the title complexes were also investigated.     

Synthesis and Crystal Structure of a Di-μ_2-phenolic Bridged Binuclear Manganese(Ⅲ) Schiff Base Complex

A new complex [Mn(L)(NCS)]2·0.5CH3CN (H2L = N,N'-bis(chlorosalicylidene)-1,2-diaminoethane) has been synthesized,and its structure (C70H51Cl8Mn4N13O8S4,Mr = 1833.84) was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system,space group C2/c with a = 25.883(2),b = 12.3320(13),c = 13.5951(16) ,β = 112.906(2),V = 3997.2(7) 3,Z = 2,Dc = 1.524 g/cm3,μ(MoKα) = 1.050mm-1,F(000) = 1852,S = 1.098,the final R = 0.0630 and wR = 0.1847 for 2542 reflections with Ⅰ 2σ(Ⅰ). The centrosymmetric title complex contains a dimer in which two distorted octahedral Mn(Ⅲ) centers are bridged equatorially by phenolic oxygen of the Schiff base ligand. The units of the complex are linked via weak C-H···N hydrogen bonds,leading to the formation of 1D chains along the b axis. The weak π-π packing interactions and weak intermolecular C(3)-H(3)···N(3) hydrogen bonds stabilize the crystal structure.     

Two Zinc（Ⅱ） Carboxyarylphosphonates with Unusual Polynuclear Zn（Ⅱ） Units：Syntheses and Crystal Structures

[Zn2(PCP)(phen)(H2O)F]n 1 and {[Zn3(MCP)2(phen)2(H2O)]·2.5H2O}n 2(PCP = p-O2C(C6H4)PO33-,MCP = m-O2C(C6H4)PO33- and phen = phenanthroline) were obtained by hydrothermal synthesis and characterized by X-ray single-crystal diffraction.Compound 1 crystallizes in the monoclinic P21/c space group with a = 7.908(2),b = 20.254(3),c = 13.477(2) ,β = 107.76(3)°,V = 2055.7(8) 3,Z = 4,C20H16FN2O6PZn2,Mr = 561.10,Dc = 1.813 g/cm3,μ = 2.463 mm-1,F(000) = 1128,the final R = 0.0340 and wR = 0.0794.Compound 2 crystallizes in the monoclinic P21/n space group with a = 15.629(3),b = 18.141(4),c = 17.723(7) ,β = 121.89(2)°,V = 4267(2) 3,Z = 4,C40H31N4O13.5P2Zn3,Mr = 1041.70,Dc = 1.620 g/cm3,μ = 1.818 mm-1,F(000) = 2108,the final R = 0.0669 and wR = 0.1775.In compound 1,the tetranuclear Zn4 units are linked together by μ4-PCP3- to build 2D(4,4) layers,which are further interconnected through the μ2-bridging fluorion into a 3D framework with 1D phen ligands-filled channels.As for the 3D supramolecular framework of 2,the novel hexanuclear Zn6 units with "chair" conformation are extended by the moieties of μ4-MCP3- ligand to a 2D(4,4) layer on the bc plane,which is viewed as the 2-folded layers in 1.In both compounds,the structures are stabilized by hydrogen bonding interactions and π-π stacking interactions between the phen rings.Additionally,FT-IR spectroscopy and the fluorescent properties are discussed.     

Synthesis and Structure of a Zinc(II) Complex:[Zn(Pybta)·Cl_2]_n

The title compound, [Zn(Pybta)Cl2]n (Pybta = 1-(2-pyridylmethyl)benzontriazole), has a zigzag chain structure. It crystallizes in the monoclinic system, space group P21/c with a = 9.0103(11), b = 17.0276(18), c = 9.2288(11) , β = 101.309(6)o, Mr = 346.51, V = 1388.4(3) 3, Z = 4, Dc = 1.658 g/cm3, F(000) = 696, μ = 2.143 mm1, the final R = 0.0492 and wR = 0.1236 for 2545 observed reflections with I > 2σ(I). The Zn atom is four-coordinated by two N and two Cl atoms, forming a slightly distorted tetrahedral geometry. Each zigzag chain links its adjacent symmetry- related equivalents via multiple π-π interactions, which are not frequently observed in the previously reported architectures.     

Two Amine-tethered Imidazolium NHC Ni(Ⅱ) Complexes: Synthesis,Structure and Catalytic Activity

Nickel(Ⅱ) complexes Ni(L1)2(1) and Ni(L2)2·CH3CN·H2O(2)(L1Cl = 2-(3-benzyl-2,3-dihydroimidazlo-1-yl)-N-(pyridin-2-yl)acetamide, chloride salt, L2Cl = 2-(3-naphthalene-2-ylmethyl)-2,3-dihydro-imidazlo-1-yl)-N-phenylacetamide, chloride salt) with amide-functionalized imidazolium NHC ligand were synthesized and determined by single-crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic system, space group P21/c with a = 9.2561(19), b = 15.138(3), c = 20.750(4) , β = 90.216(3)°, V = 2907.3(10) 3 and Z = 4. Complex 2 crystallizes in the orthorhombic system, space group Pbca with a = 15.5469(16), b = 15.3521(15), c = 31.177(3) , V = 7441.2(13) 3 and Z = 8. They are stable in the air and formed via intermolecular weak interactions, including C–H···π contacts and C–H···O hydrogen bonds. Complex 1 was applied in Suzuki coupling reaction through the investigation of reaction conditions under the optimal choice conditions: 80 ℃, K3PO4, 3% mol catalysts, 6% mol PPh3 and toluene as solvent system could afford 96% yield in 5 h.     

Synthesis, Crystal Structure and Magnetic Properties of a New Zn(II)-Nitronyl Nitroxide Complex

A new complex [Zn(NIT-1'-MeBzIm)Cl2(H2O)] (NIT-1'-MeBzIm = 2-{2'-[(l'- methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been prepared and structurally characterized by X-ray diffraction method. Crystal data: monoclinic, space group P21/n, Z = 4, C15H21Cl2N4O3Zn, Mr = 441.63, a = 7.2225(10), b = 30.849(4), c = 8.8758(13) , β = 103.904(2)°, V = 1919.6(5) 3, Dc = 1.528 g/cm3, μ(MoKα) = 1.579 mm1, F(000) = 908, R = 0.0436 and wR = 0.1029 for 2456 observed reflections with I > 2σ(I). X-ray analysis reveals that the Zn(II) ion is four-coordinated with a distorted tetrahedron. There also exist H-bonds, π-π piling interactions and weak intermolecular contacts between the NO groups which form a mutual stagger 3-D network configuration. Magnetic investigation reveals that there exists intermolecular antiferro- and ferromagnetic interactions in the title complex.     

A Novel Binuclear Cu（Ⅱ） Complex with Nitroxide Radicals Exhibiting Ferromagnetic Interactions

A new binuclear Cu(Ⅱ) complex with nitronyl nitroxide radicals [Cu(NIT3Py)2Cl2]2(NIT3Py = 2-(3'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in monoclinic,space group C2/c with a = 38.483(4),b = 7.2450(8),c = 27.559(3) ,β = 134.0180(10)°,V = 5525.6(10) 3,C48H64Cl4Cu2N12O8,Mr = 1206.00,Z = 4,Dc = 1.450 g/cm3,μ(MoKα) = 1.025 mm-1,F(000) = 2504,S = 1.066,the final R = 0.0471 and wR = 0.1121 for 3286 observed reflections(I > 2σ(I)).The title complex consists of centrosymmetric dinuclear units [Cu(NIT3Py)2Cl2]2,in which the copper ions are square-pyramidally coordinated by two pyridyl nitrogen atoms of two radical ligands and three chlorine anions,two of which bridge the copper ions.The magnetic measurements show ferromagnetic interactions between the copper ions and the radical ligands.     

Synthesis and Crystal Structure of 2,2＇-Dihydroxy-[1,1＇]binaphthalenyl-3,3＇-bis-hydroxamic Acids

The first synthesis and structural characterization by X-ray crystallography of racemic 2,2'-dihydroxy-[1,1']binaphthalenyl-3,3'-bis-hydroxamic acids were reported.The com-pound(C28H30N4O8,Mr = 550.56) crystallizes in orthorhombic system,Fdd2 space group with a = 13.055(3),b = 34.871(7),c = 12.570(3) ,V = 5722(2) 3,Z = 8,Dc = 1.278 g/cm3,λ = 0.71073 ,μ(MoKα) = 0.095 mm-1,F(000) = 2320,S = 1.021,R = 0.0349 and wR = 0.0802 for 1757 observed reflections with I > 2σ(I).The N-H and O atom are involved in two-dimensional intermolecular hydrogen bond nets,which further stabilize the structure.     

Synthesis,Structure and Luminescent Properties of [Zn(btzb)2Cl2]·2H2O[btzb=1,2-Bis(5-tetrazolyl)benzene]

The title compound[Zn(btzb)2Cl2]·2H2O(1·2H2O,btzb=1,2-bis(5-tetrazolyl)benzene)was synthesized in situ by the[2 3] cycloaddition reaction of phthalonitrile with NaN3 in water in the presence of ZnCl2 under refluxing conditions.1·2H2O crystallizes in the monoclinic system,space group P21/c with a=9.0119(18),b=7.5566(15),c=18.076(5)(A),β=114.67(2)°,V=1118.6(4)(A)3,Z=2,Dc=1.784 g/cm3 T=223(2)K,C16H16N16O2Cl2Zn,Mr=600.74,F(000)=608,μ(MoKα)=1.393 mm-1,S=1.081,R=0.0306 and wR=0.0669 for 1896 observed reflections with Ⅰ ＞2σ(Ⅰ).The Zn2 ion of 1 is coordinated by four N atoms from two btzb ligands and two Cl atoms,forming a distorted octahedral coordination geometry.A number of intermolecular hydrogen bonding interactions between molecules 1 and/or the solvated water molecules result in a 3D hydrogen-bonded structure.The luminescent property of 1·2H2O was also investigated.     

Syntheses, Crystal Structures and Characterization of Layered and Layer-pillared Zinc Arsonates

Two zinc arsonate coordination polymers, Zn(4-apa)·H2O (1, 4-apaH2 = 4-amino- phenylarsonatic acid) and Zn(4-apa) (2), have been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal and powder X-ray diffraction. Crystal data for 1: monoclinic, space group C2/c with a = 23.056(5), b = 5.4224(11), c = 15.027(3) , β = 121.22(3)°, V = 1606.6(6) ?3, Dc = 2.468 g·cm-3, F(000) = 1168, μ = 7.122 mm-1, Z = 8, the final R = 0.0309 and wR = 0.0752 for 1763 observed reflections with I > 2σ(I). For 2: monoclinic, space group P21/c with a = 8.7852(18), b = 9.2744(19), c = 9.752(2) , β = 103.45(3)°, V = 772.7(3)3, Dc = 2.410 g·cm-3, F(000) = 544, μ = 7.387 mm-1, Z = 4, the final R = 0.0321 and wR = 0.0741 for 1696 observed reflections with I > 2σ(I). The structure of 1 shows a two-dimensional (4,4)-network composed of an inorganic ladder chain bridged by the phenyl-linkers of 4-apa ligands. Compound 2 exhibits a 3D layer-pillared framework with crb net, in which inorganic (4-82)-networks are joined by the phenyl-linkers.     

Syntheses,Crystal Structures,and Antimicrobial Activities of 3-Bromo-N＇-（2- chloro-5-nitrobenzylidene）benzohydrazide and 3-Bromo-N＇-（4-nitrobenzylidene）benzohydrazide

Two new hydrazone compounds, 3-bromo-N'-(2-chloro-5-nitrobenzylidene)-ben- zohydrazide 1 and 3-bromo-N'-(4-nitrobenzylidene)benzohydrazide 2, have been synthesized and characterized by elemental analysis, IR spectra, 1H NMR, and single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic, space group P21/c with a=7.7924(10), b=24.490(3), c=7.8989(9) , β=94.987(6)°, V=1501.7(3) 3, Z=4, R=0.0345 and wR=0.0739. Compound 2 crystallizes in monoclinic, space group P21/c with a=7.4099(11), b=24.868(4), c=8.3255(12) , β=112.796(8)°, V=1414.3(4) 3, Z=4, R=0.0744 and wR=0.1912. Both compounds display E configurations with respect to the C=N double bonds. In the crystal structure of 1, molecules are linked through N-H…N and N-H…O hydrogen bonds, forming chains running along the c axis. In the crystal structure of 2, molecules are linked through N-H…O hydrogen bonds, forming chains running along the c axis. The preliminary antimicrobial activities were studied.     

A Zn(II) 5-Aminoisophthalate Coordination Polymer

The title compound, [Zn(AIP)(4,4-bipy)0.5(H2O)]n·0.75nH2O 1, was synthesized via the hydrothermal reaction of Zn(OAc)2 with 5-aminoisophthalic acid (H2AIP) and characterized by elemental analysis and infrared spectra. The complex crystallizes in monoclinic system, space group P21/c with a = 12.672(1), b = 7.6557(4), c = 16.181(1) , β = 109.187(2)o, V = 1482.6(2) 3, Z = 1, C52H52N8O23Zn4, Mr = 1418.58, Dc = 1.589 g/cm3, F(000) = 724 and μ(MoKα) = 1.685mm-1. The final R = 0.0702 and wR = 0.1524 for 1847 observed reflections with I > 2σ(I), and R = 0.0873 and wR = 0.1664 for all data. X-ray diffraction studies reveal that the title compound has an interesting 2D microporous architecture with guest water molecules inside the channel.     

Synthesis,Crystal Structure and Photoluminescence of Ethyl Coumarin-3-carboxylate Derivatives

The ethyl coumarin-3-carboxylate(1) and its two derivatives,ethyl 7-methoxy-2-oxo-2H-chromene-3-carboxylate(2) and ethyl 7-(3-methylbut-2-enyloxy)-2-oxo-2H-chromene-3-carboxylate(3),were synthesized,characterized and their UV-vis spectra and photoluminescence were investigated.Compound 2 crystallizes in the monoclinic system with space group C2/c,a = 25.884(4),b = 6.8365(11),c = 13.816(2) ,β = 104.876(2)°,V = 2362.9(7) 3,Z = 8,Dc = 1.396 g/cm3,Mr = 248.23,F(000) = 1040 and μ = 0.108 mm–1.Compound 3 crystallizes in the monoclinic system with space group P21/c,a = 15.685(6),b = 8.373(3),c = 13.063(5) ,β = 111.862(6)°,V = 1592.2(10) 3,Z = 4,Dc = 1.261 g/cm3,Mr = 302.31,F(000) = 640 and μ = 0.093 mm–1.Both the absorption and emission of the two derivatives were stronger than that of ethyl coumarin-3-carboxylate due to the larger conjugation of their electron donor group moiety at the 7-position.Under ultraviolet light excitation,the two derivatives exhibit strong blue-violet emission.     

New Efficient Copper(Ⅱ)-catalyzed Direct Access to Primary Amide from Aldehyde under Solvothermal Condition and Related Crystal Structure Study

Two 1-methyl-1H-benzo[d]imidazole derivatives, C_(18)H_(14)CuN_4O_4·C_4H_8O_2(1) and C_9H_9N_3O(2), have been synthesized and characterized by NMR, MS, FT-IR, elementary analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P2_1/n with a = 9.6888(3), b = 7.3772(2), c = 14.3277(4) ?, β = 95.819(3)°, V = 1018.81(5) ?~3, M_r = 501.98, Z = 2, D_c = 1.636 g/cm~3, F(000) = 518, μ = 1.123 mm~(-1), MoKα radiation(λ = 0.71073 ?), the final R = 0.0325 and wR = 0.0859 for 1821 observed reflections with I 2σ(I). Compound 2 crystallizes in monoclinic, space group C2/c with a = 14.2908(14), b = 14.4268(13), c = 8.4802(6) ?, β = 108.513(9)o, V = 1657.9(3) ?~3, M_r = 175.19, Z = 8, D_c = 1.404 g/cm~3, F(000) = 736, μ = 0.097 mm~(-1), Mo Kα radiation(λ = 0.71073 ?), the final R = 0.0563 and wR = 0.1531 for 1231 observed reflections with I 2σ(I). Intermolecular(N-H···N, N-H···O) and intramolecular(N-H···N, C-H···O) hydrogen bonds, as well as C-H···π and π-π stacking interactions, help to stabilize the crystal structure of compound 2.     

Syntheses and Structures of Two Ruthenium(Ⅲ) Complexes [Ru(PPh_3)_2(S_2CNR_2)Cl_2]·CH_2Cl_2(R=Et and ~iPr)

Oxidation reaction of [Ru(PPh3)3Cl2] with tetraethylthiuram disulfide [Et2NCS2]2 or tetra-iso-propylthiuram disulfide [iPr2NCS2]2 afforded ruthenium(Ⅲ) complexes [Ru(PPh3)2(S2CNR2) Cl2]·CH2Cl2(R=Et 1,iPr 2) which were characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P with a = 11.5065(6),b = 12.1458(7),c = 18.0034(9) ,α = 109.380(4),β = 95.279(4),γ = 97.969(4)°,V = 2324.8(2) 3 and Z = 2.Complex 2 belongs to the monoclinic system,space group P21/n with a = 12.5752(3),b = 20.7562(5),c = 17.6821(3) ,β = 105.934(1)°,V = 4437.94(17) 3 and Z = 4.Both mononuclear complexes 1 and 2 have an octahedral configuration around the central ruthenium atom which is bonded to one chelated dithiocarbamate ligand,two PPh3 ligands in mutually trans and two chlorides in mutually cis positions.The average Ru-S,Ru-P and Ru-Cl bond lengths are 2.377(2),2.412(2) and 2.369(2)  for 1,and 2.376(2),2.414(1) and 2.383(2)  for 2,respectively.The electrochemical properties of these two complexes were studied in CH2Cl2 solution by cyclic voltammetry.