Hydrothermal Synthesis and Crystal Structure of a New Manganese（Ⅱ） Complex with 2,4-Pyridine-dicarboxylic Acid and 2,2′-Bipyridine Ligands

A new metal-organic complex [Mn2（PDC）2（bipy）2（H2O）2] （H2PDC = 2,4-pyridine-dicarboxylic acid, bipy = 2,2′-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The compound crystallizes in triclinic, space group P ^-1 with a = 7.376（3）, b = 9.990（4）, c = 11.950（5） A^°, α= 75.217（5）, β = 78.052（5）, γ = 70.655（5）°, V = 796.0（5）A^°3, C34HE6Mn2N6O10, Mr = 788.49, De = 1.645 g/cm^3,μ（MoKa） = 0.866 mm^-1, F（000） = 235, Z = 1, the final R = 0.0425 and wR = 0.0700 for 1971 observed reflections （I 〉 2σ（I））. In the crystal structure, the manganese atom is six-coordinated by two carboxylate oxygen atoms from two different PDC ligands, one aqua ligand, and three nitrogen atoms from 2,2′-bipy and PDC ligands, giving a distorted octahedral geometry. It exhibits a three-dimensional supramolecular network defined by O-H…O hydrogen-bonding interactions.     

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Zinc（II） Complex with 2,2′-Diphenic Acid and 2,2′-Bipyridine Ligands

A new dinuclear complex [Zn(dpa)(bipy)(H2O)]2 (dpa = 2,2'-diphenic acid, bipy = 2,2'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 10.960(2), b = 9.4841(18), c = 20.599(4), β = 104.452(3)o, V = 2073.4(7)3, C48H36N4O10Zn2, Mr = 959.55, Dc = 1.537 g/cm3, μ(MoKα) = 1.225 mm-1, F(000) = 984, Z = 2, the final R = 0.0364 and wR = 0.0843 for 2788 observed reflections (I > 2σ(I)). In the crystal structure, the zinc atom is five-coordinated with two carboxylate oxygen atoms from different dpas, one coordinated water molecule and two nitrogen atoms from bipy ligands, showing a slightly distorted triangular bipyramidal geometry. Furthermore, it exhibits a zero-dimensional network structure with a sixteen-membered ring and shows yellow photoluminescent property at room temperature.     

Crystal Structure and Magnetic Property of a Two-dimensional Manganese Compound [Mn（PhCOO）2（4,4＇-bipyridine）]n

A new two-dimensional polymeric manganese compound [Mn(PhCOO)2(4,4'-bipyridine)]n 1 has been prepared and structurally characterized by X-ray diffraction. The complex crystallizes in space group Pbcn with a = 18.7158(2), b = 11.6919(3), c = 9.4799(2)(A), V = 2074.42(7)(A)3, Z = 4, Mr = 453.34, Dc = 1.452 g/cm3, μ = 0.670 mm-1 and F(000) = 932. The final refinement gave R = 0.0458 and wR = 0.1439 for 1358 observed reflections with Ⅰ＞ 2σ(Ⅰ). The complex consists of repeating units of Mn(PhCOO)2(4,4'-bipyridine). Each Mn center is sixcoordinated by four carboxylate O atoms of four benzoate anions and two pyridyl N atoms from bipy ligands to furnish a slightly distorted octahedral geometry. The two adjacent Mn atoms are connected by a pair of μ1,3-carboxylate groups to form infinite chains, which are further interlinked by bipy to complete a 2D grid network. The magnetic property of the polymeric complex has also been investigated.     

Synthesis and Crystal Structure of a 1-D Chain Zinc（Ⅱ） Coordinated Polymer with N-p-Tolysulfonyl-glutamine

A novel coordination polymer {[Zn(ts-gln)(bipy)]3H2O}n (ts-glnH2=N-p-toly-sulfonyl-glutamine,bipy=2,2-bipyridine) has been prepared and structurally characterized by X-ray diffraction method. It crystallizes in orthorhombic,space group P212121 with a=8.2622(5),b=16.6244(10),c=18.2807(10) ,V=2510.9(3) 3,C22H28N4O8SZn,Mr=573.91,Z=4,Dc= 1.518 g/cm3,μ(MoKa)=1.115 mm-1,F(000)=1192,the final R=0.0262 and wR=0.0662 for 5691 independent reflections with Rint=0.0240. The zinc(Ⅱ) atom is coordinated by N(3) and N(4) atoms of a bipy molecule,two carboxylate O(1) and O(2A) and amino N(1) atoms of ts-gln ligands,resulting in a square-pyramidal geometry. The title complex consists of an infinite zigzag chain of zinc(Ⅱ) ions linked by the carboxylate of N-p-tolysulfonyl-glutamine.     

A Two-coordinate Copper(Ⅰ) Complex Constructed from Cyanuric Acid and 4,4′-Bipyridyl:Synthesis,Structure and Photoluminescence

A two-coordinate copper(Ⅰ)complex,Cu_2(bipy)(H_2L)_2(1)(H_3L=cyanuric acid,bipy=4,4'-bipyridyl),whichexhibits strong photoluminescence,has been synthesized under hydrothermal conditions and structurally character-ized by single crystal X-ray diffraction.The compound crystallizes in the monoclinic space group P2_1/n,with cellparameters:M_r=539.42,a=13.4806(5),b=4.5234(2),c=15.4952(8),β=105.526(3)°,V=910.39(7)~3,Z=2 and μ=3.52 mm~(-1).In the structure the two Cu(Ⅰ)ions are bridged by bipy to form a two-coordinate copper(Ⅰ)dimer.The adjacent dimer units are connected by hydrogen bonding interactions,resulting in 1D zigzag chainsalong the c axis.1 emits intense yellow light when excited with UV light.     

Syntheses,Structures and Catalytic Properties of Two Mn(Ⅱ) and Cd(Ⅱ) Coordination Polymers through in Situ Ligand Reaction

Two coordination polymers, namely [Mn(μ-Hcpia)(bipy)(H_2O)_2]_n(1) and [Cd_3(μ_3-Hcpia)_2(μ-Hbiim)_2(μ-H_2biim)(H_2O)_2]_n(2), have been constructed hydrothermally using H_2cbia(H_2cbia = 5-(4'-cyanobenzoxy)isophthalic acid), bipy(bipy = 4,4'-bipyridine), H_2biim(H_2biim = 2,2'-biimidazole), and manganese or cadmium chlorides at 160℃. Interestingly, the H_3cpia(H_3cpia = 5-(4'-carboxylphenoxy)isophthalic acid) ligand was generated by in situ hydrolysis of cyano group in H_2cbia. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses(TGA), and single-crystal X-ray diffraction analyses. Both compounds crystallize in the triclinic system, space group P1. Compound 1 discloses a 1D linear chain of the 2C1 topological type. Adjacent chains are assembled into a 2D supramolecular sheet through O–H···O/N hydrogen bonds. Compound 2 features a 3D framework with a 3,4,4 T25 topology. The luminescent and catalytic properties of two compounds were investigated. Compound 1 exhibits a superior catalytic activity in the cyanosilylation at room temperature.     

Synthesis and Crystal Structure of a Novel 1D Magnesium （Ⅱ） Coordination Polymer Constructed by L-Cysteic Acid

A novel coordination polymer [Mg(L)(H2O)2]·H2O] (LH2=L-cysteic acid) has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction.The crystal crystallizes in orthorhombic system, space group P212121, with a=5.962(3), b=11.224(6), c=13.664(7)(A), V=914.3(8) (A)3, Z=4, Mr=245.50, Dc=1.783 g/cm3,μ=0.445 mm-1,flack parameter=0.32(16), F(000)=512, the final R=0.0458 and wR=0.1172 for 1578 observed reflections with I ＞ 2σ(Ⅰ). The Mg(Ⅱ) atom shows an octahedral geometry defined by two carboxyl O atoms from two different L-cysteic acid ligands, one carboxyl O atom and one amino N atom from the adjacent ligand, and two aqua ligands. The Mg(Ⅱ) atoms are bridged by L-cysteic acid ligands, leading to a 1D infinite zigzag chain. In the structure there are extensive hydrogen bonds,through which the complex completes its 3D framework structure.     

Four Complexes of Mn(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Cu(Ⅱ) Based on 2-Morpholine-4-yl-4,6-di-pyrazol-1-yl-1,3,5-triazine

Three azide bridged complexes, namely, [Mn_2L_2(N_3)_4(H_2O)_2](1), [Co_2L_2(N_3)_4]·(H_2O)_3(2) and [Ni_2L_2(N_3)_3(H_2O)]N_3·(H_2O)_4(3)(L = 2-morpholine-4-yl-4,6-di-pyrazol-1-yl-1,3,5-triazine), were synthesized by the reaction of L ligand, sodium azide with Mn(Ⅱ), Co(Ⅱ) and Ni(Ⅱ) chlorides. The copper(Ⅱ) chloride combined with thiocyanate and L ligand to form a mononuclear complex [CuL(CH_3OH)(SCN)(NCS)](4). Complexes 1~4 were characterized by IR, elemental analysis and X-ray crystallographic analysis. It was worth noting that two Mn(Ⅱ) atoms were connected by the end-to-end mode in 1, while Co(Ⅱ) and Ni(Ⅱ) atoms were connected by the end-on mode in 2 and 3. In complex 4, the central copper atom was coordinated with a sulfur atom and a nitrogen atom of the two thiocyanate ligands, respectively. Hydrogen bonds, π-π stacking interactions, thermogravimetric analysis and fluorescence properties of 1~4 were studied.     

Structural Diversity and Photoluminescent Properties of Two Mn(Ⅱ) Sulfoterephthalate Complexes from Multi-pyridine N-containing Ligands

Solvothermal reaction of manganese(II) salt with monosodium 2-sulfoterephthalate(2-NaH_2stp) and two multi-pyridine N-containing auxiliary ligands results in the formation of two new complexes formulated with [Mn_2(Hstp)_2(bpp)_2(H_2O)_4](1) and [Mn_3(stp)_2(tpy)_3(H_2O)](H_2O)_5(2)(bpp = benz-2,3-pyrimidine-[2,3-f]-1,10-phenanthroline, tpy = 2,2?:6?,2??-terpyridine). X-ray diffraction structural analyses of two complexes reveal their structural diversity(0D and 1D) due to the difference of auxiliary ligands. 1 is a discrete structure, in which the Mn(Ⅱ) ion is hexa-coordinated with one stp, one bpp ligand and two water molecules. Complex 2 is a one-dimensional(1D) chain-like structure with three crystallographically independent Mn(Ⅱ) ions. The photoluminescent properties could be assigned to the π-π* transition of 2-sulfoterephthalate ligands.     

Synthesis and Crystal Structure of a New Cadmium(Ⅱ) Polymer with One-dimensional Chain Structure: [Cd(5-hip)(phen)]n·nH2O (5-hip =5-Hydroxyisophthalate, phen = 1,10-Phenanthroline)

A new metal-organic coordination polymer [Cd(5-hip)(phen)]n.nH2O 1 has beenhydro- ermally synthesized and characterized by elemental analysis, IR, TG and single-crystal X-raydiffraction.The crystal of the complex crystallizes in monoclinic, space group P2/n with a =8.8071(17), b =12.386(2), c = 16.981(3)(A),β= 100.182(2)°, V = 1823.2(6)(A）,3, Mr= 490.73, Dc =1.788 g/cm3,μ(MoKa) = 1.240 mm-1, F(000) = 976, Z= 4, the final R = 0.0458 and wR = 0.1373 for 2864 observed reflections (I＞ 2σ(I)).The Cd atoms are coordinated by two N atoms from the phen ligands and four O atoms from 5-hydroxyisophthalate ligands in a highly distorted octahedral geometry.     

Syntheses,Crystal Structures,Magnetic and Luminescent Properties of Ni(Ⅱ), Cd(Ⅱ) and Pb(Ⅱ) Coordination Compounds Constructed from 5-Fluoronicotinic Acid

Five coordination compounds, namely [Ni_2(5-Fnic)_2(H_2 O)_4](1), [Ni(5-Fnic)(μ-5-Fnic)(H_2 biim)]n(2), {[Cd((μ-5-Fnic)2(H2 O)2]×4,4'-bipy}n(3), [Pb_2(μ-5-Fnic)_2(μ3-5-Fnic)_2(H_2 O)_2]n(4), and [Pb(5-Fnic)_2(4,4'-bipy)(H_2 O)](5), have been constructed hydrothermally using 5-FnicH(5-FnicH = 5-fluoronicotinic acid), H_2 biim(H_2 biim = 2,2'-biimidazole), 4,4'-bipy(4,4'-bipy = 4,4'-bipyridine), NiCl_2×6 H_2 O, CdCl_2×H_2 O and PbCl_2. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses(TGA), and single-crystal X-ray diffraction analyses. Structures of 1～5 range from discrete 0 D monomers(1 and 5) to 1 D coordination polymers(2 and 4) and 2 D metal-organic network(3). A broad structural diversity of 1～5 is guided by the type of the metal(Ⅱ) node and the introduction of auxiliary ligands. The magnetic(for 2) and luminescent(for 3～5) properties were also investigated and discussed.     

Synthesis and Crystal Structure of a 1-D Chain Zinc(Ⅱ) Coordinated Polymer with N-p-Tolysulfonyl-glutamine

A novel coordination polymer {[Zn(ts-gln)(bipy)]3H2O}n (ts-glnH2=N-p-toly-sulfonyl-glutamine,bipy=2,2-bipyridine) has been prepared and structurally characterized by X-ray diffraction method. It crystallizes in orthorhombic,space group P212121 with a=8.2622(5),b=16.6244(10),c=18.2807(10) ,V=2510.9(3) 3,C22H28N4O8SZn,Mr=573.91,Z=4,Dc= 1.518 g/cm3,μ(MoKa)=1.115 mm-1,F(000)=1192,the final R=0.0262 and wR=0.0662 for 5691 independent reflections with Rint=0.0240. The zinc(Ⅱ) atom is coordinated by N(3) and N(4) atoms of a bipy molecule,two carboxylate O(1) and O(2A) and amino N(1) atoms of ts-gln ligands,resulting in a square-pyramidal geometry. The title complex consists of an infinite zigzag chain of zinc(Ⅱ) ions linked by the carboxylate of N-p-tolysulfonyl-glutamine.     

Synthesis and Crystal Structure of a Novel 1D Magnesium (Ⅱ) Coordination Polymer Constructed by L-Cysteic Acid

A novel coordination polymer [Mg(L)(H2O)2]·H2O] (LH2=L-cysteic acid) has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction.The crystal crystallizes in orthorhombic system, space group P212121, with a=5.962(3), b=11.224(6), c=13.664(7)(A), V=914.3(8) (A)3, Z=4, Mr=245.50, Dc=1.783 g/cm3,μ=0.445 mm-1,flack parameter=0.32(16), F(000)=512, the final R=0.0458 and wR=0.1172 for 1578 observed reflections with I ＞ 2σ(Ⅰ). The Mg(Ⅱ) atom shows an octahedral geometry defined by two carboxyl O atoms from two different L-cysteic acid ligands, one carboxyl O atom and one amino N atom from the adjacent ligand, and two aqua ligands. The Mg(Ⅱ) atoms are bridged by L-cysteic acid ligands, leading to a 1D infinite zigzag chain. In the structure there are extensive hydrogen bonds,through which the complex completes its 3D framework structure.     

Synthesis and Fluorescent and Magnetic Properties of a New Europium Complex Eu(C_(20)H_(14)O_3N)_3(2,2'-bipy)(H_2O)·H_2O

A new europium(Ⅲ) complex Eu(C_(20)H_(14)O_3N)_3(2,2?-bipy)(H_2O)·H_2O has been synthesized with2-diphenylanine carbonyl benzoic acid and 2,2?-bipyridine as ligands.Crystal data for the complex are as follows:triclinic,space group ■,a=11.3334(5),b=16.0883(7),c=17.0116(8)?,α=70.411(4)o,β=82.435(4)o,γ=85.095(4)o,V=2894.0(2)?~3,D_c=1.484 g/cm~3,Z=2,μ=1.15 mm~(-1),F(000)=1320 and the final R=0.0447 and w R=0.0578.The Eu(Ⅲ) ion is coordinated by nine atoms to give a monocapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu~(3+):~5D_0→~7F_1 (592 nm) and ~5D_0→~7F_2 (616 nm),respectively.Also reported is the magnetic property of the complex.The complex exhibits antiferromagnetism in the temperature range of 300～2 K.     

Synthesis,Crystal Structure,Fluorescent Property and DFT Study of a Novel 1D Polymer [Zn(HMICD)(bpy)]_n·2nH_2O

A new one-dimensional(1D) polymer, [Zn(HMIDC)(bpy)]_n·2n H_2O(1, H_3MIDC = 2-methyl-imidazole-4,5-dicarboxylic acid, bpy = 2,2?-bipyridine), has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, UV-vis spectrum and fluorescence measurements. Complex 1 crystallizes in orthorhombic system, space group Pbca with a = 14.404(3), b = 8.6900(17), c = 26.570(5) ?, V = 3325.8(11) ?~3, Dc = 1.700 g/cm~3, M_r = 425.70, Z = 8, F(000) = 1744, μ = 1.522 mm~(-1), the final R = 0.0421 and w R = 0.1018. The Zn(Ⅱ) ion is six-coordinated by O and N atoms from one HMIDC ligand, two O atoms from another HMIDC ligand and two N atoms from the bpy ligand. The HMIDC anion, which acts as a tetradentate ligand, chelates two Zn ions to form a one-dimensional(1D) zigzag chain structure. We analyzed the electronic structure and orbital energies of complex 1 by DFT methods, and the results are consistent with the UV-vis spectrum. And we also discussed the luminescent mechanism of complex 1 in detail.     

Synthesis,Crystal Structure and Antitumor Activity of a Novel Zn(Ⅱ) Complex with 2-(Nicotinoyloxy)acetic Acid Ligand

A novel Zn(Ⅱ) complex, [ZnL_2(H_2O)_4]·H_2O(1, HL = 2-(nicotinoyloxy)acetic acid), was synthesized using Zn(OAc)_2·2H_2O and 2-(nicotinoyloxy)acetic acid as raw materials. Its structure has been elucidated by elemental analysis, IR and single-crystal X-ray diffraction. The structural analysis revealed that complex 1 crystallizes in triclinic, space group P1 and the Zn(Ⅱ) atom is six-coordinated with two N atoms from two different 2-(nicotinoyloxy)acetate anion ligands and four O atoms from coordinated water molecules. Complex 1 forms a 3D network structure by O–H···O hydrogen bonds. The antitumor activities of 2-(nicotinoyloxy)acetic acid ligand and its Zn(Ⅱ) complex were evaluated against human lung adenocarcinoma A549 cells, human hepatoma SMMC-7721 cells and human colon carcinoma Wi Dr cells.     

Synthesis and Crystal Structure of a One-dimensional Silver(Ⅰ) Coordination Polymer with 4,4'-Bipyridine

The title compound,{[Ag2(bipy)2(H2O2]·pydc·2H2O}n(bipy=4,4'-bipyridine,pydc=pyridine-3,5-dicarboxylate),has been synthesized by the reaction of Ag2O with pydc and bipy in CH3OH solution.It crystallizes in the monoclinic system,space group C2/c with a=21.419(8),b=7.515(3),c=18.070(7)(A),β=108.273(6)°,Mr=765.27,V=2761.9(17)(A)3,Z=4,Dc=1.840 g/cm3,F(000)=1528,μ=1.478 mm-1,the final R=0.0307 and wR=0.0681.The structure determined demonstrated that the Ag(Ⅰ)is three-coordinated by two nitrogen atoms from bipy and one water molecule,forming a one-dimensional coordination polymer[Ag2(bipy)2(H2O)2]n2n ,which is further linked to generate a two-dimensional layer structure via Ag…Ag attractions.     

SYNTHESIS AND STRUCTURE OF AN ASYMMETRIC TRICOBALT COMPOUND Co_3(o-HOC_6H_4S)_2(o-OC_6H_4S)_2(PEt_3)_3

Compound Co_3(o-HOC_6H_4S)_2(o-OC_6H_4S)_2(PEt_3)_3 was obtained by reaction of CoCl_2,o-HOC_6H_4SH(H_2mD)and PEt_3 in ethanol in the presence of NaOCH_3.The three Co atoms aretriangularly arranged and asymmetrically bridged by four S and one O atoms from the fourH_2mp ligands and terminally ligated by one O and three P atoms.Two free hydroxyl groupsform two internal hydrogen bonds with adjacent oxo donor atoms.     

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.     

Syntheses,Structures, Electrochemistry and Magnetic Properties of Two Trinuclear Cyanide-bridged Clusters Based on Tricyanometalate Building Block

The reaction of tricyanometallate precursor, Bu_4N[Fe(Tp)(CN)_3] and(Bu_4N)[(pzTp)Fe(CN)_3](Tp = tris(pyrazolyl)hydroborate, pzTp = tetrakis(pyrazolyl)borate) with Ni(ClO_4).26 H_2O in the presence of the monodentate N-methylimidazole ligand afforded two new cyano-bridged heterobimetallic {Fe2 Ni} trinuclear clusters, {[Fe(Tp)(CN)_3]_2[Ni(Mim)_4]}·8 H_2O(1) and {[Fe(pzTp)(CN)_3]_2[Ni(Mim)_4]}·2 CH_3OH·2H_2O(2). The molecular structure was determined by single-crystal X-ray diffraction. In the two compounds, the FeIII ions were coordinated by three cyanide carbon atoms and three nitrogen atoms of Tp(or pzTp) anions, whereas, the NiII ions were surrounded by two cyanide nitrogen atoms and four nitrogen atoms from four monodentate N-methylimidazole ligands, and they were bridged by tricyanometalate building block to form similar {Fe2Ni} trinuclear clusters. Cyclic voltammetry(CV) measurements indicated that compound 1 exhibited two quasireversible iron-centered reduction processes at –0.71 and –0.17 V and one quasireversible nickel-centered oxidation process at 0.92 V, while compound 2 showed two quasireversible iron-centered reduction processes at –0.66 and –0.09 V and one quasireversible nickel-centered oxidation process at 0.88 V. Magnetic measurements showed that compounds 1 and 2 exhibited strong intrachain ferromagnetic interaction between the low-spin Fe~Ⅲ(S = 1/2) and high-spin Ni~Ⅱ(S = 1) ions.