Crystal Structure and Magnetic and Fluorescent Properties of a New Copper（II） Complex Cu2（L）4（2,2＇-bipy）2（H2O）2

A new copper（II） complex Cu2（L）a（2,2＇-bipy）2（H2O）2 （1） has been synthesized with 2-benzoylbenzoic acid （HL） and 2,2＇-bipyridin as ligands. The crystal belongs to a monoclinic system with space group Cc, a = 13.9979（II）, b = 15.9888（13）, c = 30.306（3） A, β = 100.8700（10）°, V= 6661.1（10） A3, Dc= 1.372 g/cm3, Z = 8, F（000） = 2840, the final GOOF = 1.018, R= 0.0685, and wR= 0.1731. There are two mononuclear Cu（L）2（2,2＇-bipy）（H20） units in the crystal of 1. Each Cu（II） cation is coordinated by five atoms. The magnetic and fluorescent properties of 1 were studied. The results show that 1 exhibits weak paramagnetism, and when the excitation wavelength is at 616 nm, it has an intense fluorescent emission band around 482 nm.     

Syntheses and Structures of Two New Cobalt Supramolecular Complexes, [Co（4,4＇-bipy）2（H2O）4]·[Co2（4,4＇-bipy）3（H2O）8]·2TST·2（4,4＇-bipy）·4H2O and [Co（4,4＇-bipy）2（H2O）4]DSNT·4,4＇-bipy

Two new cobalt（II） supramolecular complexes [Co（4,4＇-bipy）2（H2O）4]·[Co2（4,4＇-bipy）3（H2O）8]·2TST·2（4,4＇-bipy）·4H2O 1 and [Co（4,4＇-bipy）2（H2O）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 （H3TST） and 2,4-bis（p-sulfanilato）-6-diethylamino-1,3,5-triazine （H2DSNT）, 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 P21/n with a = 13.599（4）, b = 18.988（6）, c = 22.995（7） A, β = 90.273（6）°, V = 5938（3）A^3, Z = 4, C56H59Co1.5N13O17S3, Mr = 1370.74, Dc = 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 〉 2σ（I）. The crystal structure of 2 belongs to the monoclinic system, space group C2/c with a = 18.864（6）, b = 14.283（5）, c = 20.246（7）A, β = 107.799（6）°, V = 5194（3）A^3, Z = 4, C49H52CoN12O10S2, Mr = 1092.08, Dc = 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.     

Syntheses and Crystal Structures of Two New Metal Phosphonates： [Mn（H2O）2（C12H8N2） （HO3PCH2CH2CO2） ] and [Co（H2O）4（C10H8N2）]-（HOaPCH2CH2CO2）

By the reactions of manganese（if） acetate, 2-sulfoethylphosphonic acid, 1,10-phen （1,10-phen = 1, 10-phenanthroline） or cobalt（Ⅱ） acetate, 4,4＇-bipy and 2-carboxyethylphosphonic acid, two novel compounds of [Mn（H2O）2（C12H8N2） （HO3PCH2CH2CO2） ] （1） and[Co（H2O）4（C10H8N2）]-（HOaPCH2CH2CO2） （2） have been synthesized and characterized by IR spectroscopy, elemental analyses and single-crystal X-ray diffraction. Compound 1 has a 0D structure. Two Mn（ii） ions are linked by two 2-carboxyethylphosphonic acid ligands, forming a centrosymmetric dimer. These dimers are further interlinked into a 2D layer structure by π-π stacking interactions and hydrogen bonds. Compound 2 has a 1D chain structure. The 2-carboxyethylphosphonic acid remains uncoordinated and acts as the organic template. By the bridge of 4,4＇-bipy, the [Co（4,4＇-bipy）]^2＋ chains are formed.     

Synthesis and Structure of a Novel Supramolecular Compound E Co（ 2,2＇-bipy） （ H20 ） 4] E trans-1,4-chdc ] and Separation of Isomer of 1,4-Cyclohexanedicarboxylic Acid

A supramolecular compound, [ Co（2,2＇-bipy） （ H2O）4 ] [ trans-1,4-chdc ] （ compound 1 ） （ 2,2＇-bipy = 2,2＇- bipyridine, 1,4-chdcH2 = 1,4-cyclohexanedicarboxylic acid）, was synthesized and characterized by single-crystal Xray diffraction analysis, IR spectrometry, TG analysis, and elemental analyses. Single-crystal X-ray diffraction analysis revealed that [ Co（ 2,2＇-bipy） （ H2O）4 ]^2＋ units and adjacent 1,4-chdc^2- formed a single layer by hydrogen bonding and electrostatic interactions along the ac-plane, and two symmetry-related single layers interacted with each other by hydrogen bonding, resulting in a double layer, which further formed a 3-D structure by π-π stacking. The most attractive structural feature of compound 1 is that 1,4-chdc2- possesses only tram-conformation although there are both c/s- and tram-conformations in the raw material.     

Synthesis, Crystal Structure and Electrochemical Properties of One-dimensional Chain Coordination Polymer [Co（Ⅱ）（C6H5CH=CHCOOH）2（4,4＇-bipy）（H2O）5]n

A one-dimensional chain coordination polymer [Co（Ⅱ）（C6H5CH--CHCOOH）2（4,4＇- bipy）（H20）5]n has been synthesized with cinnamylic acid, 4,4＇-bipy and cobaltous chloride as raw materials. Crystal data for this complex： monoclinic, space group P21/c, a = 1.1481（3）, b = 1.1230（2）, c = 1.1759（3） nm, β = 97.054（4）^o, V= 1.5046（6） nm^3, Mr= 617.50, Dc = 1.363 g/cm^3, Z = 2, ,u（MoKa） = 0.627 mm^-1, F（000） = 646, S = 1.062, R 0.0443 and wR = 0.1178. The crystal structure shows that two neighboring cobalt（ID ions are linked together by one 4,4＇-bipy, and the whole complex molecule adopts a one-dimensional chain structure. Each cobalt（H） ion is coordinated with two nitrogen atoms from two 4,4＇-bipy molecules and four oxygen atoms from four water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were analyzed by combining with the crystal structure.     

Synthesis and Crystal Structure of a Ni（Ⅱ） Complex of 2＇-[4-N,N＇-（Dimethylaminobenzyl- idene）]-3,5-dihydroxybenzoylhydrazide and Its Spectral Properties

A new nickel（II） complex [NiL2]（DMF）4 （HL = 2＇-[4-N,N＇-（dimethylamino- benzylidene）]-3,5-dihydroxybenzoylhydrazide） has been synthesized and its structure was characterized by IR,UV-Vis,1H NMR and elemental analysis. The fluorescence emission mechanism of the complex was discussed by fluorimetric spectra. The single-crystal structure was determined by X-ray diffraction analysis. The crystal belongs to the triclinic system,space group P1 with a = 0.9918（4）,b = 1.1297（4）,c = 1.1331（4） nm,α = 76.860（7）,β = 75.105（6）,γ = 89.022（7）°,V = 1.1936（8） nm^3,Z = 1,μ = 0.472 mm^-1,Dc = 1.319 g/cm^3,F（000） = 502 and Rint = 0.0913. In the title compound,the nickel（II） atom is four-coordinated with two nitrogen atoms from amide and two oxygen atoms from keto group. The complex is centrosymmetric with nickel located at the center.     

Hydrothermal Processing,Characterization and Theoretical Calculations of a Copper（Ⅱ） Compound with 1,10-Phenanthroline Derivative Ligand：2-（4-Methoxyphenyl）-1H-imidazo[4,5-f][1,10] Phenanthroline

The metal-organic compound [Cu(MOPIP)2(OH)2] 1(MOPIP = 2-(4-methoxy-phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline) was hydrothermally synthesized and structurally characterized by elemental analysis,Fourier-transformed infrared spectroscopy,thermogravimetric analysis,single-crystal X-ray diffraction and theoretical calculations in Gaussian 03.In the crystal structure,the copper(Cu) atoms are tetra-coordinated with four different nitrogen atoms from two different MOPIP ligands,and the Cu atom is one of the five vertexes of the tetrahedron.Presumably due to the steric bulk of the phenyl ligands,compound 1 adopts a slightly distorted tetrahedral configuration.Moreover,it exhibits a zero-dimensional structure with Cu-MOPIP as the building units.Natural Bond Orbital(NBO) analysis was performed by using the NBO method built in Gaussian 03 Program.The calculation results showed a covalent interaction between the coordinated atoms and Cu(Ⅱ) ion.     

Synthesis and Crystal Structure of N-Benzyl-N＇-（2-pyridyl）urea and Its Mononuclear Cu（Ⅱ） Complex

A new ligand of N-benzyl-N＇-（2-pyridyl）urea L and its self-assembly product with CuCl2, [Cu（Ⅱ）LCl2]∞ 1, have been synthesized and structurally characterized by IR, 1H NMR and single-crystal X-ray diffraction analysis. In the structure of L, the urea groups adopt Z,E conformation to form dimers through intermolecular hydrogen bonds; while in complex 1, it assumes Z,Z conformation to fit for the coordination sphere of the Cu（Ⅱ） ions. The coordinated units are connected through intermolecular N-H...Cl hydrogen bonds to form an extended 2D framework. Finally, a 3D structure is obtained via π-π stacking interactions between pyridyl rings     

Syntheses and Crystal Structures of Three Novel Zn~Ⅱ-sulfonyldibenzoilate Coordination Polymers

Three coordination polymers based on the V-shaped 4,4＇-dicarboxybiphenyl sulfone （H2sdba） ligands, [Zn3（μ-OH）2（sdba）2]n·2nH2O 1, [Zn2（sdba）2（4,4＇-bipy）]n·2nH2O 2 and [Zn3（sdba）3（py）2]n·n（py）·nH2O 3 （4,4＇-bipy = 4,4＇-bipydine）, were hydrothermally synthesized and structurally characterized. Complex 1 features the 2D planes constructed by the sdba ligands linking infinite Zn-O-C SBUs. The 4,4＇-bipy ligands in 2 bridge the Zn^II-sdba chains into interpenetrated 2D planes. The 3D network of α-Po topology in 3 is built from tri-nuclear Zn3 units with a [Zn3（OOC）6] structure. The intense blue and yellow luminescence was observed in complexes 1～3 which may result from ligand-to-metal charge transfer （LMCT）.     

A Novel Layered Complex with Rhomboidal Channels:Hydrothermal Synthesis, Crystal Structure, and Properties of Cu(4,4′-bipy)2(H2PO4)2(H2O)2 (bipy=bipyridine)

The combination of both 4,4′-bipyridine(4,4′-bipy) and dihydrogen phosphate anion ligands with copper(Ⅱ) results in the formation of a novel layered compound Cu(4,4′-bipy)2(H2PO4)2(H2O)2. The crystal structure comprises discrete neutral Cu(4,4′-bipy)2(H2PO4)2(H2O)2 units. The copper atom, located on the crystallographic twofold axis, is coordinated with two nitrogen atoms of terminal 4,4′-bipy ligands and two water molecules at the equatorial positions, and two dihydrogen phosphate oxygen atoms at the axial positions, forming an elongated octahedron. The complex is a two-dimensional distorted rhomboidal network possessing two kinds of rhomboids with dimensions of ca. 1.6792 nm×0.3203 nm and 1.2778 nm×0.3198 nm, respectively. The two-dimensional networks are stacked parallelly on each other along c-axis to give an extended three-dimensional channel network with an interlayer distance of ca. 0.5030 nm. Crystal data: triclinic, space group P-1, a=1.0253(2) nm, b=1.4501(3) nm, c=0.79715(16) nm, α=97.91(3)°, β=90.99(3)°, γ=85.54(3)°, V=1.1703(4) nm3, Z=2, R=0.0892, wR=0.2451.     

Synthesis,Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn （NAA ）2（ 4,4′-bipy ） （H2O）4]n

A novel one-dimensional chain coordination polymer [Mn（NAAh（4,4′-bipy）（H2O）4], has been synthesized with a-naphthaleneacetic acid, 4,4′-bipy and manganese（Ⅱ） sulfate as raw materials. Crystal data for this complex： monoclinic, space group P21/c, a = 1.1421（2）, b = 1.6337（3）, c = 0.94177（19） nm, β = 112.15（3）°, V = 1.6275（6） nm^3, De = 1.407 g/cm^3, Z = 2, μ（MoKa） = 0.467 mm^-1, F（000） = 722, S = 1.007, R= 0.0412 and wR = 0.1022. The crystal structure shows that two neighboring manganese（Ⅱ） ions are linked together by one 4,4′-bipy molecule, and the whole complex molecule forms a one-dimensional chain structure. Each manganese（Ⅱ） ion is coordinated with two oxygen atoms of two a-naphthaleneacetic acid molecules, two nitrogen atoms of two 4,4′-bipy molecules and two oxygen atoms from two water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were also analyzed.     

Hydrothermal Synthesis and Crystal Structure of a New One-dimensional Cobalt（Ⅱ） Complex with 2-Pyridinecarboxyic Acid and 4,4＇-Bipyridine Ligands

A new metal-organic coordination polymer [Co（2-pya）2（4,4＇-bipy）]2n-[（4,4＇- bipy）0.5· H2O]2n （2-pya = 2-pyridinecarboxylic acid, 4,4＇-bipy = 4,4＇-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in tetragonal, space group I41/a with a = b = 22.719（2）, c = 10.710（2）/k, V = 5527.8（14） A3, C54H46N10Co2O10, Mr= 1112.87, Dc = 1.337 g/cm3,μ（MoKa） = 0.665 mm-1, F（000） = 2296, Z = 4, the final R = 0.0633 and wR = 0.1096 for 1261 observed reflections （I 〉 2σ（I））. It exhibits a one-dimensional chain-like structure constructed by mixed ligands of 2-pyridinedicarboxylic acid and 4,4＇-bipyridine.     

Hydrothermal Synthesis,Crystal Structure and Magnetic Property of a Novel Mixed Valence Decatungstate： [Cu（2,2＇-bipy）2]2Na2W6^VW4·VIO30·2H2O

A novel Cu（II）-2,2＇-bipy-supported （bipy = bipyridine） mixed valence decatungstate, [Cu（2,2＇-bipy）2]2Na2W6^VW4^VIO30·2H2O 1, has been synthesized and structurally characterized by X-ray analysis. The crystal of 1 is of triclinic, space group P1^- with a= 10.9393（10）, b = 12.0492（2）, c = 12.3783（2）A, a = 80.631（10）, β= 70.226（10）, γ= 72.329（9）^o, V = 1459.64（4）A^3, Z = 1, Dc = 3.582 g/cm^3, F（000） = 1404, R = 0.0553 and wR = 0.1242 for 4607 observed reflections （I 〉 2σ（I））. The EPR spectrum of 1 indicates that its unpaired electrons are placed in the dx2-y2 orbital of the ground state of Cun. Furthermore, compound 1 shows an antiferromagnetic interaction.     

Crystal Structure and Thermal Stability Properties of a New 1D Chain Cu（ll） Coordination Polymer with 2,3-Pyridinedicarboxylic Acid as the Ligand

A new 1D chain copper coordination polymer [CuE（H2L）2（C10HsN2）（HEO）2]n＇3n（H20） with 2,3-pyridinedi carboxylic acid （H2L） and 2,2＇-bipyridine （2,2＇-bipy） as ligands has been synthesized in the mixed ethanol and water solvents. Crystal data for this complex are as follows： monoclinic, space group P2Jc, a = 7.7713（7）, b = 27.478（3）, c = 13.2621（13）/1,, fl = 100.6940（10）, V= 2782.8（5） A3, Dc = 1.722 g/cm3, Z = 4, p = 1.61 mm-1, F（000） = 1472, the final R = 0.0363 and wR = 0.0933. In the crystal structure, the whole molecule consists of two cooper ions, two H2L, one 2,2＂-bipy molecule and six water molecules. Each central copper ion is coordinated with three oxygen atoms from two H2L and one water molecule, two nitrogen atoms from one 2,2＇-bipy molecule and two H2L, giving a distorted tetragonal pyramidal geometry. Thermal stability properties of the complex were investigated.     

Synthesis, Crystal Structure and Fluorescene of a One-dimensional Compound {CdI_2(2,2′-bipy)}_n

The title compound, {CdI2(2,2′-bipy)}n, was prepared by the hydrothermal reac- tion of CdI2 and 2,2′-bipy in an aqueous solution, and its crystal structure was determined by X-ray single-crystal analysis. Crystallographic data for 1: C10H8N2CdI2, monoclinic system, space group C2/c, a = 16.927(1), b = 10.0925(7), c = 7.7422(3) , β = 106.0629(4)°, V = 1271.00(14) 3, Z = 4, F(000) = 944, μ = 6.546 mm-1, Dc = 2.730 g/cm3, Mr = 522.38, the final R = 0.0309 and wR = 0.0805 for 1310 observed reflections (I > 2σ(I)). X-ray crystal structure analysis shows that the Cd atom is coordinated by four iodines and two N atoms from one 2,2′-bipy to form an 1-D chain-like structure through bridging iodines. The fluorescene of the title compound was also discussed.     

Hydrothermal Synthesis, Structure and Thermal Stability of a Copper Coordination Polymer Bridged by Pimelic Acid

A novel one-dimensional chain copper（Ⅱ） coordination polymer { [Cu（2,2′-bipy）- （HPDA）]（HPDA）（H2O）}n has been hydrothermally synthesized using pimelic acid, 2,2′-bipyridine and copper perchlorate in the mixture of water and methanol. The crystal structure was determined as a monoclinic system, space group P21/c, with a= 1.01139（14）, b = 2.6898（4）, c = 1.02105（14）, β = 109.651（2）°, V = 2.6159（6） nm^3, Dc = 1.412 g/cm^3, Z = 2, F（000） = 1164, GOOF = 1.044, R = 0.0570 and wR = 0.1448. The copper ion is coordinated with two nitrogen atoms of one 2,2′- bipyridine molecule and three oxygen atoms from two heptane diacid molecules, forming a distorted square-pyramidal geometry. The result of TG analysis shows that the title complex is stable under 200.0 ℃.     

Synthesis, Characterization and Properties of Tri-substitute Potassium Salt of Trinitrophloroglucinol

The title complex [K3（TNPG）·（H2O）2]n was synthesized by the reaction of the aqueous solutions of trinitrophlomglucinol （TNPG） with KHCO3. The complex was characterized by elemental analysis and FTIR spectroscopy, and its single crystal structure was determined by X-ray diffraction analysis. The structural analysis demonstrates that two different coordination modes of K cations [K（1） and K（2）] are around TNPG^3- anions in complex [Ka（TNPG）·（H2O）2]n, where the coordination numbers are eight. All K atoms coordinate with O atoms of phenolic hydroxyl group and nitro-group simultaneously. The thermolysis of the [Ka（TNPG） · （H2O）2]n has been investigated by using differential scanning calorimetry （DSC） and thermogravimetry-derivative thermogravimetry （TG-DTG） at a heating rate of 10 ℃/min. The thermal decomposition processes of the title complex were comprised of one endothermic dehydration stage and one exothermic decomposition stage in 270-320℃, and the final decomposition residue contained KNC. Impact and friction sensitivity results of the complex revealed its sensitive nature towards mechanical stimuli. The experiments verified that the complex has some characteristics of explosive.     

Synthesis, Dimeric Crystal Structure, and Biological Activities of N- （ 4-Methyl-6-oxo-1,6-dihydro-pyrimidin-2-yl ） -N＇- （ 2-trifluoromethyl-phenyl ） -guanidine

The title compound, N-（4-methyl-6-oxo-1,6-dihydro-pyrimidin-2-yl）-N＇-（2-tritluoromethyl-phenyl）-guanidine, was synthesized and its structure was confirmed by using IR, MS,^1H NMR, and elemental analysis. The single crystal structure of the title compound was determined by X-ray diffraction. The preliminary biological test showed that the synthesized compound has a weak herbicidal activity.     

STUDY ON THE STRUCTURE AND SPECTRA OF BINUCLEAR BRIDGED COMPLEX μ-4,4-bipy [VO(acac)_2]_2

The synthesis and ~1H NMR, ESR, IR, UV spectra of binuclear bridged complex μ-4,4-bipy[VO-(acac)_2]_2 are reported in this paper. The structure of the complex is discussed using measured spectral parameters.It is deemed that 4,4-bipy as a bridge passing through its two N atoms combined respectively with two V atoms at its sixth position, forming a binuclear bridged complex.The spectra are explained satisfactorily and coefficients of molecular orbitals,β_1,β_2 and 8_m,are calculated from the results of ESR and UV etc.     

In Situ Hydrothermal Synthesis of a Mononuclear Copper（Ⅱ） Complex： Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-Hydroxyl-5-sulfoisophthalic Acid）

The mononuclear complex, Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-hydroxyl- 5-sulfoisophthalic acid and bpy = 2,2＇-dipyridyl）, has been synthesized by the hydrothermal reaction of Cu（OH）2 with NaH2SIP and bpy at 160 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectrum. The new ligand 4-hydroxyl-5-sulfoisophthalic acid derived from 5-sulfoisophthalic acid ligand under an in situ hydrothermal condition. The crystal of the complex crystallizes in a triclinic system, space group P1, with a = 7.757（4）, b = 10.663（6）, c = 11.727（7）A, α = 94.272（4）, β = 104.067（7）, γ = 97.400（7）°, V= 927.4（9）A^3, Z = 2, C18H14N2O9SCu, Mr= 497.93, Dc= 1.783 g/cm^3,μ = 1.350 mm^-1, F（000） = 506, the final R = 0.0518 and wR = 0.1513 for 4180 observed reflections with I 〉 2σ（I）. The central Cu（II） ion is five-coordinated by two oxygen atoms from the H2SIP-O^2- ligand and two nitrogen atoms of bpy ligand in a distorted square-planar geometry as well as a water oxygen atom in the apical position to complete a distorted square-pyramidal coordination geometry. The mononuclear copper molecules are linked by hydrogen bonds between coordinated water molecules and sulfonate groups to form a one-dimensional double-chain structure. The chains are further held together through extensive π-π stacking interactions between the aromatic rings to form a three- dimensional supramolecular structure.