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.     

A highly stable and luminescent mononuclear Cu(Ⅰ) bis-{5-tert-butyl-3-(6-methyl-2-pyridyl)-1H-1,2,4-triazole} complex

A new emissive mononuclear homoleptic Cu(Ⅰ) complex of 5-rert-butyl-3-(6-methyl-2-pyridyl)-1H-1,2,4-triazole(bmptzH),[Cu(bmptzH)_2](ClO_4)(1),has been synthesized by treatment of[Cu(PPh_3)_2(CH_3CN)_2](ClO_4) or [Cu(CH_3CN)_4](ClO_4) with the bmptzH ligand.It is revealed that complex 1 displays a distorted N_4 tetrahedral arrangement formed by two bmptzH chelates,in which bmptzH adopts a neutral bidentate chelating coordination mode using the N atom of the pyridyl ring and the 4-N not 2-N atom of the 1,2,4-triazolyl ring.It is shown that complex 1 is highly stable and exhibits good luminescence properties in solution and solid states at room temperature due to the introduction of a methyl group at the ortho-position of the pyridyl ring.     

Halogen Mediated Self-assembly of Three Mixed Valent Cu(Ⅰ)/Cu(Ⅱ) Complexes

Reaction of the ligand dmpt(dmpt=6,7-dimethylbenzo[f][1,10]phenanthroline)with CuCl_2 afforded mixed valent Cu(Ⅰ)/Cu(Ⅱ) discrete tetranuclear complexes[Cu(Ⅱ)Cl_2(dmpt)Cu(Ⅰ)Cl](1),while the reaction of ligand dppz(dppz = dipyrido[3,2-a:20,30-c]phenazine) with divalent halogen copper salt CuX_2(X=Cl,Br) gave one-dimensional chain mixed valent Cu(Ⅰ)/Cu(Ⅱ) complexes [Cu(Ⅱ)Cl_2(dppz)Cu(Ⅰ)Cl]_n(2) and discrete mixed valent Cu(Ⅰ)/Cu(Ⅱ)complexes [Cu(Ⅱ)Br_2(dppz)(DMF)Cu(Ⅰ)Br](3). Complex 2 consists of a one-dimensional chain-dppzC u(Ⅱ)-Clμ_2-Cu(Ⅰ)-Cl-dppzC u(Ⅱ)-Clμ_2-Cu(Ⅰ)-with Cu(Ⅱ) and Cu(Ⅰ) atoms linked together by chloride anion. Complex 3 is a discrete complex,which is the same as complexes 1 and 2 involving two different copper valent Cu(Ⅰ) and Cu(Ⅱ). The Cu(Ⅰ) ion presents a pseudo-trihedral geometry,while the Cu(Ⅱ) ion presents a slightly distorted square-pyramidal geometry. This fact proved that halogen ions play a vital role in the assembly procedure. Our research results demonstrate the structural diversification that can be achieved by halogen ions mediated. Moreover,halogen ions-mediated self-assembly may provide useful information for further design of compounds with novel structures and properties.     

Synthesis and Characterization of a New Symmetric Dinucleating Ligand and Its Dizinc(Ⅱ)Complex with Alkoxo and Carboxylate Bridges

<正>A novel dinuclear zinc(Ⅱ)complex[Zn_2L(μ-OAc)](PF_6)_2(CH_3OH)has been synthesized from a new symmetrical compartmental ligand HL in which the pendant arms,bearing pyridyl groups,are bridged by 1,3-diaminopropan-2-ol.X-ray crystal structure shows that the two zinc atoms reside within the adjacent ligand compartments and are bridged by the endogenous alkoxo-O from ligand and one exogenous carboxylate from acetate with a syn-syn mode.The coordination geometry of two zinc atoms is a distorted trigonal bipyramid with the pyridyl-N atoms and bridging alkoxo-O atom providing the equatorial donor set.Such coordination geometry observed in this complex is similar to that found in the dinuclear unit of phospholipase C.     

Trinuclear Cu(Ⅱ) and Zn(Ⅱ) complexes bridged by μ_3-carbonato anion

The trinuclear Cu(Ⅱ) and Zn(Ⅱ) complexes [(CuTPA)_3(μ3-CO_3)] (ClO_4)_4(1) and [(ZnTPA)_3(μ_3-CO_3)] (ClO_4)_4 (2) (TPA=tri(pyridylmethyl) amine) have been synthesized. X-ray structure analysis of the two complexes proves that CO_3~(2-) anion has an unusual triply bridging ligand, bridging three CuTPA and ZnTPA units respectively, and assembles new trinuclear complexes. The CO_3_(2-) comes from atmospheric CO_2. The structure of each trinuclear unit consists of three copper or zinc atoms in a five-coordinate triangular bipyramidal environment. The [(CuTPA)_3 (μ_3-CO_3)] (ClO_4)_4 compound shows a very weak antiferromagnetic coupling.     

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 and Crystal Structures of Two New Complexes Generated from 2-((Pyridin-3-ylmethyl)thio)-5-(6-quinolinyl)-1,3,4-oxadiazole and Ag~Ⅰ Salts

Two new Ag~Ⅰ-complexes have been synthesized based on the semi-rigid ligand 2-((pyridin-3-ylmethyl)thio)-5-(6-quinolinyl)-1,3,4-oxadiazole(L),obtained by the condensation reaction of 5-(6-quinolinyl)-1,3,4-oxadiazole-2-thiol and 3-chloromethyl pyridine hydrochloride. Crystallization of L with Ag OTf and Ag PF_6 in a CH_2Cl_2/MeO H mixed solvent system at room temperature affords a novel supramolecular [Ag_2L_2(CF_3SO_3)_2](I) and a coordination polymer [Ag L(PF_6)]_n(Ⅱ),respectively. Two complexes were characterized by TGA,X-ray powder and single-crystal diffraction.     

Syntheses and Anti-lung Cancer Activities of Zn(Ⅱ) and Cu(Ⅱ) Complexes Based on Triazole and Tetrazole,respectively

The reactions of 4H-1,2,4-triazole(Htrz) with ZnCl_2, 1H-tetrazole(Htez) and Cu(NO_3)2·6H_2O afford two novel coordination polymers respectively, {[Zn_2(trz)_2(ox)](H_2O)_3}n(1) and {[Cu_3(tez)_3(OH)_2(H_2O)_2](NO_3)(DMF)_4}_n(2)(H_2ox =(COOH_)2, DMF = N,N-dimethylformamide). 1 shows 1D channels along the a axis filled with water molecules and 2 features a 2D bi-layered framework based on trinuclear Cu(II) units bridged by two μ3-OH groups. In addition, in vitro antitumor activities of compounds 1 and 2 on four human lung cancer cells(16HBE, NCI-H1299, NCI-H460 and NCI-H292) were further determined.     

In Situ Synthesis,Structural Characterization and Catalytic Properties of a 2D Cu(Ⅰ)-cyanide Coordination Polymer

A new Cu(Ⅰ) coordination polymer(CP) formulated as [Cu_2(L)(CN)_2]_n(1, L =1,1?-bis(5,6-dimethylbenzimidazole)methane) was synthesized, in which the cyanide anions were generated in situ by the cleavage of C–C bond of acetonitrile under hydrothermal conditions. CP 1 was characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. It crystallizes in the orthorhombic system, Pccn space group, with a = 10.314(3), b = 20.966(7), c =9.432(3) ?, V = 2039.5(11) ?~3, Z = 4, C_(21) H_(20) Cu_2 N_6, M_r = 483.51, D_c = 1.575 g×cm~(-3), μ = 2.105 mm~(-1) and F(000) = 984, the final R = 0.0608 and wR = 0.1942 for 1226 observed reflections with Ⅰ 2s(Ⅰ)for the CP 1. The CP 1 possesses a 2D {63} layer structure which is composed of Cu(Ⅰ) centers bridged by L and CN– ligands. The thermal stability and luminescence properties of CP 1 are discussed in detail. The complex also displays a remarkable activity for the degradation of methyl orange by hydrogen peroxide in a Fenton-like process.     

Synthesis,Crystal Structure and Properties of a New Binuclear Copper(Ⅱ) Complex with 5-Oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic Acid(TNCA)

A new binuclear copper(Ⅱ) complex [Cu_2(Hpt)_2(TNCA)_2(H_2O)_2]·4 H_2O(1) has been synthesized with copper acetate, 5-oxo-4-oxa-tricyclo[4.2.1.0]nonane-9-carboxylic acid(TNCA) and 3-(pyridin-2-yl)-1,2,4-triazole(Hpt). It crystallizes in the triclinic space group P~-_1, with a = 8.8199(18), b = 14.278(3), c = 15.269(3) ?, α = 76.21(3)o, β = 81.07(3)o, γ = 76.07(3)o, V = 1802.7(6) ?~3, Dc = 1.636 g/cm~3, Z = 2, F(000) = 916, the final GOOF = 1.051, R = 0.0556 and wR = 0.1388. The whole molecule consists of two copper ions bridged by two μ_2-η~1:η~0-3-(pyridin-2-yl)-1,2,4-triazole anions. The coordination environment of the Cu(1) ion is CuO_2N_3, giving a distorted square pyramidal geometry. 1 exhibits antiferromagnetic interaction between Cu(Ⅱ) ions, the electron transfer of 1 is irreversible in electrode reactions and the TG analysis shows that 1 is stable below 440 K.     

Synthesis and Crystal Structure of a Cu(Ⅱ) Coordination Polymer: [Cu(L)(1,10-phen)]_n

A new complex [Cu(L)(1,10-phen)]n(1, L = N-3-pyridine sulfonyl amino acid) has been synthesized and characterized by IR, elemental analysis and X-ray diffraction analysis, and its crystal belongs to monoclinic, space group P21/c with a = 11.481(2), b = 18.094(4), c = 8.5198(17) , β = 102.26(3)°,V = 1729.5(6) 3, Z = 4, Dc = 1.759 g/cm3, F(000) = 932, μ = 1.422 mm-1, R = 0.0368 and wR = 0.0893. In 1, the Cu(Ⅱ) ion adopts a slightly distorted five-coordinated square pyramidal geometry. The L2- ligand adopts O of the carboxyl bridging adjacent Cu(Ⅱ) units to form an infinite chain structure along the c axis. Also, π-π stacking interactions between the adjacent chains expanded the 1-D structures into a 3-D supramolecular structure.     

Hydrothermal Synthesis,Crystal Structure and Properties of a New Copper(Ⅱ) Coordination Polymer with 3-(2-Pyridiyl)-1H-1,2,4-triazole(Hpt)

A new copper(Ⅱ) coordination polymer [Cu_2(C_7H_5N_4)_2(3-C_6H_5NO_2)_2]_n(1) has been hydrothermally synthesized with copper hydroxide, 3-(pyridin-2-yl)-1,2,4-triazole(Hpt) and 3-pyridinecarboxylic acid(3-PCA). It crystallizes in the monoclinic space group C2/c, with a=16.854(2), b=7.8616(8), c=20.630(2) ?, β=111.126(2)o, V=2549.7(5) ?3, Dc=1.723 g/cm3, Z=8, F(000)=1336, the final GOOF=1.065, R=0.0380 and w R=0.0972. The whole molecule consisting of two copper ions are bridged by two μ_2-η~1:η~0-3-(pyridin-2-yl)-1,2,4-triazole anions. The coordination environment of Cu(1) ion is CuO_2N_4, giving a distorted octahedron geometry. 1 exhibits antiferromagnetic interaction, and the electron transfer of 1 is irreversible in electrode reactions and the TG analysis shows that 1 is stable below 235 ℃.     

A Cu(Ⅱ) Complex with IM-MeImz-к2 N,O Mode in [Cu(IM-MeImz)2]·(SCN)2: Synthesis, Crystal Structure and Magnetic Properties

A new copper(Ⅱ) compound with imino nitroxide radicals [Cu(IM-MeImz)2]·(SCN)2 (IM-meImz =2-(5-methylimidazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl) has been synthesized and characterized structurally and magnetically. It crystallizes in monoclinic, space group P21/c with a = 9.3604(7), b = 10.3012(7), c = 16.6684(12) (A), β = 105.0290(10)°, V = 1552.25(19)(A)3, C24H34CuN10O2S2, Mr = 622.27, Z = 2, Dc = 1.331 g/cm3, μ(MoKα) = 0.876 mm-1, F(000) =650, the final R = 0.0374 and wR = 0.1079. X-ray analysis demonstrates that the IM-MeImz ligand is coordinated to the copper(Ⅱ) ion as an unusual didentate chelate with a κ2 N(MeImz),O(IM) mode in the complex. The square-planar coordination sites at Cu(Ⅱ) are occupied by two O and two N atoms from the imino nitroxide radicals. The complex molecules are connected as a onedimensional polymer structure by intermolecular interactions. Magnetic measurements show that there are intramolecular antiferromagnetic interactions between the Cu(Ⅱ) ion and radicals.     

Self-assembly of a Mixed-valence Cu(Ⅰ)/Cu(Ⅱ) Coordination Polymer Derived from a Conformationally Flexible Tripodal Phosphoric Trimide Ligand

Reaction of a tripodal ligand, N,N?,N??-tris(3-pyridinyl) phosphoric trimide(TPPA) and CuBr_2·2H_2O result in the assembly of a new polymeric copper coordination polymer, which was characterized by single-crystal diffraction, infrared spectroscopy and elemental analysis. The polymer crystallizes in the triclinic system, space group P1 with a = 9.0964(5), b = 10.2592, c = 10.5822(8) ?, V = 933.01(9) ?~3, Z = 2, C_(30)H_(24)Br_4Cu_3N_(12)O_2P_2, M_r = 985.02, D_c = 1.753 g/cm~3, F(000) = 4072 and μ(MoKα) = 0.746 mm~(-1). The final R and w R are 0.0588 and 0.1329 for 4260 observed reflections with I 2σ(I). Cu(Ⅰ) is tetrahedrally coordinated and Cu(Ⅱ) center adopts square planar coordination geometry. Because of the flexibility of the TPPA ligands, the pyridyl rings rotate though a certain angle and three pyridyl rings on the same TPPA rotate by about 45° with respect to the central P=O groups. TPPA ligand acts as a tridentate ligand and is coordinated with three metal centers with its pyridyl donors to form a 2D-sheet like structure, and it is further connected by N–H···O and N–H···Br, resulting in a 3D network packing. Oxidation states of the metal center have been determined by bond valence sum calculation.     

HETERONUCLEAR COMPLEX CONTAINING COPPER-LANTHANIDE ARRAYS: THE SYNTHESIS AND CRYSTAL STRUCTURE OF Ln_2Cu_4L_8 (HL)_4(OH)_2(CIO_4)_4(H_2O)_(10)·2CH_3COCH_3 (Ln = Tb (1), Y (2); HL = 2-Pyridone C_5H_5NO)

Reaction of 2-pyridone, copper acetate and terbium(or yttrium) perchlorate in acetone with the moleratio 6: 2: 1 results in the formation of heteronuclear complex Ln_2Cu_4L_8 (HL)_4 (OH)_2 (ClO_4)_4 (H_20)_(10)2CH_3COCH_3(Ln = Tb (1), Y (2)). By recrystallizing (1) in CHCl_3 single crystals were obtained and thestructure was determined by four-circle diffractometer. Data showed that the crystal is in space groupC2/m with a=27. 454(9)A, b=13, 608A, c=30. 556(11)A, β=99. 89(3)°, v=11245. 7(7. 5)A~3. Thestructure was solved by a combination of Patterson method and Fourier technique. The final R value is0. 103. In the structure, four copper and two terbium ions are bridged by 2-pyridone anions to form anessentially octahedral Cu_4Tb_2 core. The terbium atoms are each eight-coordinate and the copper atomsare five-coordinate.     

Two Discrete Cu-Complexes Constructed from a Multidentate N-Containing Dinucleating Ligand

Two comparable discrete complexes [CuⅡ(CH3CN)2L2]·2(ClO4) 1 and [CuI2I2L2]·(DMF)2 2 were successfully synthesized by the reaction of CuⅡ and CuⅠ salts with a novel dinucleating ligand 2,5-bis(3-pyridinylmethylthio)-1,3,4-thiadiazole)(L),respectively.Complex 1 presents a single nuclear structure while 2 has a dimeric structure where two CuI ions are doubly bridged by halide ions in a μ2-fashion.Both discrete molecules were outspreaded into a one-dimensional supramolecular chain via aromatic interactions such as C-H…π and π…π interactions.     

A Double Azole-bridged Dinuclear Copper(Ⅱ) Complex Containing 4-Pyridyl-NH-1,2,3-triazoles: Synthesis,Structure and Magnetism

A new dinuclear copper(Ⅱ) compound [Cu_2(CH_3COO)_2(L)_2(H_2O)_2]·4H_2O(1, HL = 4-pyridyl-NH-1,2,3-triazole) has been synthesized and characterized. Single-crystal X-ray diffraction showed that complex 1 crystallizes in monoclinic space group P2_1/c with a = 0.8427(1), b = 1.0981(1), c = 1.3610(1) nm, β = 93.364(4)°, V = 1.2573(1) nm~3, M_r = 643.56, Z = 2, D_c = 1.700 g/cm~3, μ = 1.760 mm~(-1), R = 0.0376, wR = 0.0981, and possesses a planar Cu_2N_4 six-membered ring, in which both Cu(Ⅱ) ions are bridged by two 1,2,3-triazole ligands. The neighboring dinuclear molecules are bound by strong intermolecular hydrogen bonds to create 1-D chains expanding along the b axis, which further form a 3-D supramolecular framework. Magnetic susceptibility measurement indicated the presence of weak antiferromagnetic interactions within the complex. The best fit using spin Hamiltonian yields the magnetic coupling constant J = –14.82 cm~(-1) above 30 K. The magnetic data are compared to those obtained for related double diazine bridged dinuclear copper(Ⅱ) complexes and magnetostructural correlations are discussed.     

STUDY ON THE STRUCTURES OF COORDINATION COMPOUNDS OF N-(ortho-METHYL)-AND N-(ortho-METHOXY)-PHENYL IMINODIACETATO-Cu(Ⅱ)

The coordination compounds,{Cu[CH_3C_6H_4N(CH_2COO)_2]}.2H_2O and{Cu[CH_3OC_6H_4N(CH_2COO)_2]}.2H_2O,have been prepared and its crystal struc-tures determined.The final discrepancy factors are R=0.052,R_w=0.061 for(I)and R=0.052,R_w=0.039 for(Ⅱ).The geometry of the coordination poly-hedron with Cu(Ⅱ)is a distorted tetragonal pyramid for(Ⅰ)and an unsym-metrical and extended tetragonal bipyramid for(Ⅱ),respectively.The re-sults of EHMO calculations indicate that the ligand mainly provided thefield with very few of its electrons being coordinated to the central atom.     

Direct Electrochemical Synthesis and Crystal Structure of a New Mononuclear Copper(Ⅱ) Complex: [(bipy)2Cu(PhCOO)]ClO4·(benzil) (benzil = 1,2-Diphenyl-ethane-1,2-dione)

A new mononuclear copper(Ⅱ) complex [(bipy)2Cu(PhCOO)]ClO4·(benzil) (bipy=2,2'-bipyridine, benzil=1,2-diphenyl-ethane-1,2-dione) was synthesized by direct electrochemical oxidation of Cu electrode in an acetonitrile solution with benzoic acid, 2,2'-bipyridine and benzoin. As soon as the current flowed in the cell, benzoin was oxidized to benzil quickly. The crystal structure was determined by X-ray diffraction. It belongs to monoclinic system, space group P21/c with a=14.860(2), b=20.784(3), c=11.9150(17) (A), β=101.401(3)°, V=3607.3(9) (A)3, Z=4, Mr=806.69, Dc=1.485 g/cm3, F(000)=1660, μ=0.742 mm-1, R=0.0788 and wR=0.1519 for 6254 observed reflections (Ⅰ ＞ 2σ(Ⅰ)). The complex contains a mononuclear [(bipy)2Cu(PhCOO)] cation, a solvate benzil molecule and a ClO4- anion which locates around the cation outside acting as the counter ion. The Cu(Ⅱ) ion is coordinated by two 2,2'-bipyridines and one benzoato ligand to form a distorted square-pyramid.     

Synthesis,Crystal Structure and Magnetic Properties of Heptanuclear Manganese Complexes with Schiff-base Ligand

One new mixed-valence heptanuclear manganese complex, [Mn~ⅡMn~Ⅲ6O_2L_6-(NaCH_3COO)_2(CH_3COO)_4](1)(L = 3-ethoxy-6-(((2-hydroxyethyl)imino)methyl) phenol, was synthesized by treating the Schiff-base ligand with Mn(acac)_3?4H_2O and characterized by elemental analysis, IR spectra, thermogravimetric analyses and X-ray single-crystal diffraction. 1 has a similar new mixed-valence heptanuclear structure. The magnetic measurements indicate that 1 exhibits the antiferromagnetic interactions.