A novel coordination polymer of [Co( p-CPOA)(2,2′-bipy)(H2O)]n ( p-CPOA2-=4-carboxylphenoxyacetate dianion, 2,2′-bipy=2,2′-bipyridine) was synthesized and characterized by elemental analysis, IR and X-ray single cr...A novel coordination polymer of [Co( p-CPOA)(2,2′-bipy)(H2O)]n ( p-CPOA2-=4-carboxylphenoxyacetate dianion, 2,2′-bipy=2,2′-bipyridine) was synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction. The title complex crystallizes in monoclinic space group C2/c, with a=1.424 4(3) nm, b=1.316 6(3) nm, c=1.947 7(4) nm, β=104.56(3)°. V=3.535 3(14) nm3, Z=8, R=0.028 5, wR=0.089 1. The cobalt(Ⅱ) ion displays a distorted octahedral coordination geometry, defined by three carboxyl oxygen atoms from different p-CPOA2- groups, two nitrogen atoms from 2,2′-bipyridine ligand and one water molecule. The cobalt atoms are bridged by p-CPOA2- groups, forming a one-dimensional chain structure along a axis. The adjacent Co...Co atoms distance is 0.996 8 nm. A layer supramolecular network is contrsucted by the hydrogen bonds and π-π stacking interactions. CCDC: 220039.展开更多
Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of th...Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of these complexes in pyridine at different temperature. These complexes could activate molecular oxygen and were used as catalysts in cyclohexene oxidation. The influence of ligand structure on the dioxygen affinity and catalytic activity of the complexes were discussed.展开更多
The novel three-dimension edta-linked （edta--ethylenediamine-N,N,N＇,N＇-tetraacetate） heterometallic complex [Sba（edta）2-μ4-Co（H20）2]·5.15H2O has been synthesized and characterized by elemental analyses, ...The novel three-dimension edta-linked （edta--ethylenediamine-N,N,N＇,N＇-tetraacetate） heterometallic complex [Sba（edta）2-μ4-Co（H20）2]·5.15H2O has been synthesized and characterized by elemental analyses, FT-IR spectrum, X-ray diffraction analyses and thermogravimetry-differential scanning calorimetry （TG-DSC）. The complex crys- tallizes in the monoclinic system, space group P21/n, lattice parameters： a=0.69969（2） nm, b=2.08705（4） nm, c-- 1.08106（2） nm, β=90.031（1）°, V=1.57866（6） nm3, Z=2, Mr=1007.76, Dc=2.120 g-cm 3 F（000）=1001,μ= 2.323 mm t, the final R=0.0235 and wR--0.0629 for 3480 observed reflections [l〉2σ（l）]. In the structure each Co（II） ion is connected with Sb（III） ions bridging by four carboxylic oxygen atoms, and in each [Sb（edta）] anion, the Sb（III） ion is six coordinated by two nitrogen and four oxygen from edta ions, together with a lone electron pair at the equatorial position. In the complex, the coordination number of Co（II） ion is six and its coordination environment is composed of four carboxylic oxygen atoms from four different edta ions and two oxygen atoms from two H2O molecules. The degradation of the sample proceeds in several steps and the water molecules and ligands are successively emited.展开更多
A new cobalt（II） complex [Co（NO2-salen）2]·1.5H2O containing mono acetalization Schiff base ligand（NO2-salen = N-5-nitro-salicylideneamino ethanato） has been prepared through one-pot template condensation, a...A new cobalt（II） complex [Co（NO2-salen）2]·1.5H2O containing mono acetalization Schiff base ligand（NO2-salen = N-5-nitro-salicylideneamino ethanato） has been prepared through one-pot template condensation, and has been structurally characterized by elemental analysis, IR spectra and X-ray diffraction. It is formulated as C18H23CoN6O7.5, crystallizes in the hexagonal system, space group of R-3c with α = 25.895（18）, b = 25.895（18）, c = 35.075（6）, γ = 120o, V = 20368（3） and Z = 36. The ligand of 5-nitrosalicylaldehyde-ethylene-diamine takes unusual mono asymmetry mode. The Co（II） ion exhibits a coordination number of six, and assumes a distorted octahedral geometry with a N2O4 donor set. The neutral monomeric units of [Co（NO2-salen）2]·1.5H2O are linked into a one-dimensional（1D） structure via the intermolecular hydrogen bonds and weak π-π stacking interactions. Cyclic-voltammetry measurement reveals the oxidation and reduction processes for the complex are irreversible in nature.展开更多
The title compound, Co（L）2（CH3OH）2Cl2 （L = 3-（1,2,4-triazole-yl）-6-chloro-pyridazine） 1, has been synthesized and its crystal structure has been determined by X-ray analysis. Complex 1 crystallizes in the tric...The title compound, Co（L）2（CH3OH）2Cl2 （L = 3-（1,2,4-triazole-yl）-6-chloro-pyridazine） 1, has been synthesized and its crystal structure has been determined by X-ray analysis. Complex 1 crystallizes in the triclinic system, space group P1 with a = 6.018（3）, b = 9.832（5）, c = 9.921（5）A, a = 78.270（8）, β = 74.550（8）, γ = 83.807（8）°, V = 553.1（5）A^3, Z = 1, C14H16Cl4CoN10O2, Mr = 557.10, Dc = 1.673 g/cm^3, F（000） = 281,μ（MoKα） = 1.293 mm^-1, the final R = 0.0453 and wR = 0.1181 for 1539 observed reflections with I 〉 2σ（I）. The Co（II） ion is in a distorted centrosymmetric six-coordinate octahedral environment with two Ntriazole, two Omethanol and two Cl atoms. Via hydrogen bonds the configuration of 1 has been extended into 1D chains which are developed to 2D layers via π-π sticking action, and these layers are further extended into a 3D network by hydrogen bonds. The antibacterial activity of the title compound has been detected, and the results show that the ligands and cobalt（II） complex exhibit certain fungicidal activity against several bacteria. Furthermore, the spectral properties of the title compound have been also studied and discussed.展开更多
A novel dinuclear complex with an empirical formula [Co2(1H-benzimidazole)4(1, 4-bdoa)2] (1,4-bdoa2– = benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR and single-cry...A novel dinuclear complex with an empirical formula [Co2(1H-benzimidazole)4(1, 4-bdoa)2] (1,4-bdoa2– = benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 11.000(2), b = 19.385(4), c = 11.417(2) ?, β = 95.49(3)o, V = 2423.3(8) ?3, Z = 2, Mr = 1074.77, Dc = 1.473 g/cm3, μ = 0.760 mm–1, F(000) = 1108, the final R = 0.0645 and wR = 0.0714 for 3273 observed reflections (I > 2σ(I)). Two octahedrally coordinated Co(II) atoms are bridged by two 1,4-bdoa2– groups, generating a macrocyclic ring complex. The Co…Co separa- tion is 7.677(3) ?. An extended 3-D supramolecular network is formed through hydrogen bonds and weak π-π stacking interactions.展开更多
A novel dinuclear complex [Co2(atr)3(mal)2(H2O)2]·4H2O(1) (atr = 4-amino-1,2,4-triazole and mal = malonic acid) containing mixed N and O-donor atoms has been prepared and structurally characterized. The structure...A novel dinuclear complex [Co2(atr)3(mal)2(H2O)2]·4H2O(1) (atr = 4-amino-1,2,4-triazole and mal = malonic acid) containing mixed N and O-donor atoms has been prepared and structurally characterized. The structure is made up of the symmetrically 1, 2, 4-triazole bridged [Co2(atr)3(mal)2(H2O)2] moiety and four lattice water molecules. The single crystal X-ray analysis reveals that the complex has a distorted octahedral structure. Magnetic susceptibility measurements reveals that antiferromagnetic interactions exists between the high spin Co(II) ions within the dinuclear unit.展开更多
A fluorescent cobalt（II） complex, 1 [Co（H2bibim）2（5-nipa）], for the recognition of cations and small molecules constructed with 5-nitroisophthalic acid （5-H2nipa） and 2,2＂-biben- zimidazole （H2bibim） has be...A fluorescent cobalt（II） complex, 1 [Co（H2bibim）2（5-nipa）], for the recognition of cations and small molecules constructed with 5-nitroisophthalic acid （5-H2nipa） and 2,2＂-biben- zimidazole （H2bibim） has been synthesized by hydrothermal methods and structurally characterized by elemental analysis, IR spectroscopy, PL and single-crystal X-ray diffraction. The cobalt units are six-coordinated by two H2bibim ligands and one 5-nitroisophthalic acid group, which are further connected into a three-dimensional （3D） network by intermolecular hydrogen bonds. Complex 1 exhibits fluorescence and thus has detection capabilities for different cations and small solvent molecules in the solution state at room temperature.展开更多
A dinuclear cobalt（II） complex [Co2（a-furacrylato）4（Phen）2（H20）]＇C2HsOH has been synthesized with a-furacrylic acid and 1,10-phenanthroline as the ligands, and its crystal structure was determined. The crysta...A dinuclear cobalt（II） complex [Co2（a-furacrylato）4（Phen）2（H20）]＇C2HsOH has been synthesized with a-furacrylic acid and 1,10-phenanthroline as the ligands, and its crystal structure was determined. The crystal is of monoclinic system, space group C2/c with a = 1.07388（8）, b = 2.4300（2）, c = 1.86708（14） nm, β= 104.3830（10）°, V= 4.719.4（7） nm3, Dc = 1.503 g/cm3, Z = 2, F（000） = 2196, GOOF = 1.053, the final R = 0.0343 and wR = 0.0883. The crystal structure shows that two neighboring cobalt（II） ions are linked by the bridging coordination of two a-furacrylic acid anions and one water molecule, and their end positions are respectively coordinated with two 1,10-phenanthroline molecules and two a-furacrylic acid anions, forming a dinuclear structure. Both cobalt（II） ions adopt hexa-coordinated distorted octahedral geometry. The electrochemical and fluorescence properties of the title complex are also discussed.展开更多
The reaction of anhydrous cobalt(II) dichloride with 1-methylimidazoline-2(3H)- thione in dichloromethane solution gave the title complex, [Co(C4H6N2S)2Cl2]. X-ray single-crystal analysis revealed that the complex c...The reaction of anhydrous cobalt(II) dichloride with 1-methylimidazoline-2(3H)- thione in dichloromethane solution gave the title complex, [Co(C4H6N2S)2Cl2]. X-ray single-crystal analysis revealed that the complex crystallizes in a monoclinic system, space group P21/c, a = 13.9707(10), b = 10.0435(7), c = 10.3910(6) ?, β = 91.181(3)o, V = 1457.70(17) ?3, Z = 4, C8H12Cl2N4S2Co, Mr = 358.17, Dc = 1.632 g/cm3, μ = 1.813 mm–1, F(000) = 724, the final R = 0.0710 and wR = 0.1224 for 1549 observed reflections with I > 2σ(I). The Co atom is coordinated by two S atoms from two 1-methylimidazoline-2(3H)-thione ligands and two chloride ions in a slightly distorted tetrahedral geometry. The intramolecular classical hydrogen-bonding interactions involving chloride ions and N–H groups of the heterocyclic thione ligands are observed. The offset π-π stacking interactions between the imidazole rings of adjacent molecules with a face-to-face dis- tance of 3.604 ? are found in the packing diagram.展开更多
A new polymeric cobalt complex [Co(-male)(py)(H2O)]n (male = maleate; py = pyridine) 1 was prepared by cobalt chloride hexahydrate with disodium maleate and pyridine in an alcohol-aqueous solution. Single-crystal X-ra...A new polymeric cobalt complex [Co(-male)(py)(H2O)]n (male = maleate; py = pyridine) 1 was prepared by cobalt chloride hexahydrate with disodium maleate and pyridine in an alcohol-aqueous solution. Single-crystal X-ray analysis has revealed that 1 crystallizes in the orthor- hombic system, space group Pnma with a = 18.001(1), b = 7.6001(6), c = 7.4731(6) ? V = 1022.4(1) 3, Z = 4, C9H9CoNO5, Mr = 270.10, Dc = 1.755 g/cm3, F(000) = 548, m(MoK? = 1.683 mm-1, S = 1.002, the final R = 0.0280 and wR = 0.0746 for 883 observed reflections with I > 2s(I). The structure analysis shows an approximate octahedral coordination environment of metal center. The Co(II) ions are bridged by maleic anions in a rare tetradentate coordination fashion with a syn-anti coplanar con- formation of the carboxyl group, forming a two-dimensional corrugated 2-D structure which is further attached into a three-dimensional framework via non-classical CH…O interactions between adjacent layers.展开更多
A new cobalt(II) complex, [Co(H2 oxado)3 ]C2 O4 H2 oxado·2H2 O (H2 oxado = oxamide dioxime), has been synthesized in aqueous solution and characterized by elemental analysis and single crystal X-ray structure det...A new cobalt(II) complex, [Co(H2 oxado)3 ]C2 O4 H2 oxado·2H2 O (H2 oxado = oxamide dioxime), has been synthesized in aqueous solution and characterized by elemental analysis and single crystal X-ray structure determination. The complex crystallizes in the triclinic space group P-1, with the parameters a = 9.46(4), b = 11.84(5), c = 12. 81(5)?Å, α = 104.94(6), β = 99.29(5), γ = 106.73(5), V = 1284(9) Å3, Z = 2. The central cobalt(II) cation is pseudo-octahedrally coordinated by six imino N atoms of the neutral oxamide dioxime ligand. In the solid state, each of the following bricks, namely the cationic complexes, the oxalate dianions as well as the oxamide dioxime crystallization molecules, pile up parallel to the a axis. The bulk structure is consolidated by an extended three-dimensional network of hydrogen bridgings—that link the ionic partners, oxamide dioxime and water molecules to one another—and by coulombic interactions.展开更多
A new hydrogen bonded Cobalt(II) Schiff base complex,?N’-(pyridine-4-carboxaldehyde) isonicotinoylhydrazone Cobalt(II), has been synthesized from isoniazid and pyridine-4-carboxaldehyde and characterized by IR spectr...A new hydrogen bonded Cobalt(II) Schiff base complex,?N’-(pyridine-4-carboxaldehyde) isonicotinoylhydrazone Cobalt(II), has been synthesized from isoniazid and pyridine-4-carboxaldehyde and characterized by IR spectroscopy, 1H-NMR, elemental analysis, TGA and single crystal X-ray structure determination. X-ray crystal structure analysis shows an octahedral complex with a metal centre coordinated to two ligand molecules through the pyridine nitrogen atoms and four water molecules and containing two nitrate groups as counter ions. The complex crystallizes in the monoclinic crystal system and P2(1)/n space group. The unit cell dimensions are: a = 7.2108(4) Å, b = 16.6020(9) Å, c = 13.0389(6) Å,α = 90°, β = 103.972(4)°, γ = 90°. The molecule is symmetrical about the cobalt centre as observed from the 1H-NMR and 13C-NMR and confirmed by the single crystal X-ray structure of the complex. Thermogravimetric analysis shows two steps decomposition of the complex to leave a metal oxide residue. The title compound is expected to be biologically active as one of the precursors (isoniazid) is a therapeutic agent with well-established clinical applications.展开更多
A monomeric complex [Co(Im)(2)(O2CMe)(2)] (1) and a novel aqua-bridged dimeric complex 1 [Co-2(mu-H2O)(mu-O2CMe)(2)(Im)(4)(O2CMe)(2)] (2) (Im = imidazole) have been synthesized and characterized. Complexes 1 and 2 coe...A monomeric complex [Co(Im)(2)(O2CMe)(2)] (1) and a novel aqua-bridged dimeric complex 1 [Co-2(mu-H2O)(mu-O2CMe)(2)(Im)(4)(O2CMe)(2)] (2) (Im = imidazole) have been synthesized and characterized. Complexes 1 and 2 coexisted in solution. Pure forms of either complex can be obtained from the same solution by controlling the crystallization conditions. All two complexes possess a carboxylate-Im-cobalt(II) triad system analogous to the carboxylate-histidine-metal triad systems that have been found in many zinc enzymes and cobalt(II)-substituted enzymes. In 2, two Co2+ ions are connected by a water molecule in a bridging fashion with (CoCo)-Co-... [0.3687(1) nm], Co-OH2-[0.2159(3) nm], and Co-OH2-Co [117.2(3)degrees], in which the water molecule is further stabilized by two intramolecular hydrogen bonds with the oxygens of the terminal monodentate acetate groups with the distance of (OO)-O-... [0.2609(7) nm]. The terminal monodentate acetate groups display quite abnormal geometry due to the strong 'pulling effect' on the carboxylates by intermolecular and intramolecular hydrogen bonds. Complex 2 showed weak antiferromagnetic coupling at low temperature with g = 2.22 and J = - 1.60 cm(-1).展开更多
Two one-dimensional cobalt（II） compounds {[Co（Hbpma）（H20）4]2·3SO4·4.5H2O}n 1 and {[Co（Hbpma）（NCS）3（H20）]·2.85H2O}n 2 （bpma = N,N＇-bis（3-pyridylmethyl）amine） have been synthesized and st...Two one-dimensional cobalt（II） compounds {[Co（Hbpma）（H20）4]2·3SO4·4.5H2O}n 1 and {[Co（Hbpma）（NCS）3（H20）]·2.85H2O}n 2 （bpma = N,N＇-bis（3-pyridylmethyl）amine） have been synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group Pi with a = 15.8780（5）, b = 16.2187（5）, c = 16.4858（5） A, α = 91.0420（10）,β = 94.5190（10）, γ = 101.4360（10）°, V = 4145.7（2） A3, C24H53Co2N6024.5083, Mr = 1031.76, Z = 4, Dc = 1.653 g/cm3, p（MoKa） = 1.046 mm-1, F（000） = 2148, S = 1.017, the final R = 0.0269 and wR = 0.0644 for 13032 observed reflections （I 〉 2a（/））. For complex 2, it belongs to triclinic, space group Pi with a = 9.3761（11）, b = 10.5814（13）, c = 11.2972（14）A, α= 85.472（2）,β = 88.058（2）,γ = 76.203（2）°, V= 1085.0（2） A3, C15Hzl.v0CoN603.85S3, Mr= 502.79, Z = 2, Dc = 1.539 g/cm3, p（MoKa） = 1.112 mm-1, F（000） = 519, S = 1.070, the final R = 0.0358 and wR = 0.0899 for 3466 observed reflections （I 〉 2σ（I））. Two complexes 1 and 2 are both found to be one-dimensional coordination polymers bridged by the protonated bpma ligands, which are assembled into three-dimensional supramolecular structures through the hydrogen bonding interactions and π-π packing interactions.展开更多
文摘A novel coordination polymer of [Co( p-CPOA)(2,2′-bipy)(H2O)]n ( p-CPOA2-=4-carboxylphenoxyacetate dianion, 2,2′-bipy=2,2′-bipyridine) was synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction. The title complex crystallizes in monoclinic space group C2/c, with a=1.424 4(3) nm, b=1.316 6(3) nm, c=1.947 7(4) nm, β=104.56(3)°. V=3.535 3(14) nm3, Z=8, R=0.028 5, wR=0.089 1. The cobalt(Ⅱ) ion displays a distorted octahedral coordination geometry, defined by three carboxyl oxygen atoms from different p-CPOA2- groups, two nitrogen atoms from 2,2′-bipyridine ligand and one water molecule. The cobalt atoms are bridged by p-CPOA2- groups, forming a one-dimensional chain structure along a axis. The adjacent Co...Co atoms distance is 0.996 8 nm. A layer supramolecular network is contrsucted by the hydrogen bonds and π-π stacking interactions. CCDC: 220039.
文摘Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of these complexes in pyridine at different temperature. These complexes could activate molecular oxygen and were used as catalysts in cyclohexene oxidation. The influence of ligand structure on the dioxygen affinity and catalytic activity of the complexes were discussed.
文摘The novel three-dimension edta-linked （edta--ethylenediamine-N,N,N＇,N＇-tetraacetate） heterometallic complex [Sba（edta）2-μ4-Co（H20）2]·5.15H2O has been synthesized and characterized by elemental analyses, FT-IR spectrum, X-ray diffraction analyses and thermogravimetry-differential scanning calorimetry （TG-DSC）. The complex crys- tallizes in the monoclinic system, space group P21/n, lattice parameters： a=0.69969（2） nm, b=2.08705（4） nm, c-- 1.08106（2） nm, β=90.031（1）°, V=1.57866（6） nm3, Z=2, Mr=1007.76, Dc=2.120 g-cm 3 F（000）=1001,μ= 2.323 mm t, the final R=0.0235 and wR--0.0629 for 3480 observed reflections [l〉2σ（l）]. In the structure each Co（II） ion is connected with Sb（III） ions bridging by four carboxylic oxygen atoms, and in each [Sb（edta）] anion, the Sb（III） ion is six coordinated by two nitrogen and four oxygen from edta ions, together with a lone electron pair at the equatorial position. In the complex, the coordination number of Co（II） ion is six and its coordination environment is composed of four carboxylic oxygen atoms from four different edta ions and two oxygen atoms from two H2O molecules. The degradation of the sample proceeds in several steps and the water molecules and ligands are successively emited.
基金supported by the National Natural Science Foundation of China(No.21273101)the Foundation of the Program for Backbone Teachers in Universities of Henan Province(No.2012GGJS158)+1 种基金tackle key problem of science and technology Project of Henan Province(No.142102310483)the Foundation of Education Committee of Henan Province(No.14B150033)
文摘A new cobalt（II） complex [Co（NO2-salen）2]·1.5H2O containing mono acetalization Schiff base ligand（NO2-salen = N-5-nitro-salicylideneamino ethanato） has been prepared through one-pot template condensation, and has been structurally characterized by elemental analysis, IR spectra and X-ray diffraction. It is formulated as C18H23CoN6O7.5, crystallizes in the hexagonal system, space group of R-3c with α = 25.895（18）, b = 25.895（18）, c = 35.075（6）, γ = 120o, V = 20368（3） and Z = 36. The ligand of 5-nitrosalicylaldehyde-ethylene-diamine takes unusual mono asymmetry mode. The Co（II） ion exhibits a coordination number of six, and assumes a distorted octahedral geometry with a N2O4 donor set. The neutral monomeric units of [Co（NO2-salen）2]·1.5H2O are linked into a one-dimensional（1D） structure via the intermolecular hydrogen bonds and weak π-π stacking interactions. Cyclic-voltammetry measurement reveals the oxidation and reduction processes for the complex are irreversible in nature.
文摘The title compound, Co（L）2（CH3OH）2Cl2 （L = 3-（1,2,4-triazole-yl）-6-chloro-pyridazine） 1, has been synthesized and its crystal structure has been determined by X-ray analysis. Complex 1 crystallizes in the triclinic system, space group P1 with a = 6.018（3）, b = 9.832（5）, c = 9.921（5）A, a = 78.270（8）, β = 74.550（8）, γ = 83.807（8）°, V = 553.1（5）A^3, Z = 1, C14H16Cl4CoN10O2, Mr = 557.10, Dc = 1.673 g/cm^3, F（000） = 281,μ（MoKα） = 1.293 mm^-1, the final R = 0.0453 and wR = 0.1181 for 1539 observed reflections with I 〉 2σ（I）. The Co（II） ion is in a distorted centrosymmetric six-coordinate octahedral environment with two Ntriazole, two Omethanol and two Cl atoms. Via hydrogen bonds the configuration of 1 has been extended into 1D chains which are developed to 2D layers via π-π sticking action, and these layers are further extended into a 3D network by hydrogen bonds. The antibacterial activity of the title compound has been detected, and the results show that the ligands and cobalt（II） complex exhibit certain fungicidal activity against several bacteria. Furthermore, the spectral properties of the title compound have been also studied and discussed.
基金This work was supported by the National Natural Science Foundation of China (No. 20101003), Natural Science Foundation of Heilongjiang Province (No. B0007) and the Scientific Fund of Remarkable Teachers of Heilongjiang Province (1054G036)
文摘A novel dinuclear complex with an empirical formula [Co2(1H-benzimidazole)4(1, 4-bdoa)2] (1,4-bdoa2– = benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 11.000(2), b = 19.385(4), c = 11.417(2) ?, β = 95.49(3)o, V = 2423.3(8) ?3, Z = 2, Mr = 1074.77, Dc = 1.473 g/cm3, μ = 0.760 mm–1, F(000) = 1108, the final R = 0.0645 and wR = 0.0714 for 3273 observed reflections (I > 2σ(I)). Two octahedrally coordinated Co(II) atoms are bridged by two 1,4-bdoa2– groups, generating a macrocyclic ring complex. The Co…Co separa- tion is 7.677(3) ?. An extended 3-D supramolecular network is formed through hydrogen bonds and weak π-π stacking interactions.
文摘A novel dinuclear complex [Co2(atr)3(mal)2(H2O)2]·4H2O(1) (atr = 4-amino-1,2,4-triazole and mal = malonic acid) containing mixed N and O-donor atoms has been prepared and structurally characterized. The structure is made up of the symmetrically 1, 2, 4-triazole bridged [Co2(atr)3(mal)2(H2O)2] moiety and four lattice water molecules. The single crystal X-ray analysis reveals that the complex has a distorted octahedral structure. Magnetic susceptibility measurements reveals that antiferromagnetic interactions exists between the high spin Co(II) ions within the dinuclear unit.
基金supported by the National Natural Science Foundation of China(No.51062016)the Major Project of Science Research & Technology Exploitation of Guangxi Province(11107013-8)
文摘A fluorescent cobalt（II） complex, 1 [Co（H2bibim）2（5-nipa）], for the recognition of cations and small molecules constructed with 5-nitroisophthalic acid （5-H2nipa） and 2,2＂-biben- zimidazole （H2bibim） has been synthesized by hydrothermal methods and structurally characterized by elemental analysis, IR spectroscopy, PL and single-crystal X-ray diffraction. The cobalt units are six-coordinated by two H2bibim ligands and one 5-nitroisophthalic acid group, which are further connected into a three-dimensional （3D） network by intermolecular hydrogen bonds. Complex 1 exhibits fluorescence and thus has detection capabilities for different cations and small solvent molecules in the solution state at room temperature.
基金Supported by the Fund of Science and Technology Committee of Hunan Province(No.2012GK3030)the Scientific Research Fund of Hunan Provincial Education Department(No.B21018)the Hengyang Bureau of Science & Technology(No.2011kG28)
文摘A dinuclear cobalt（II） complex [Co2（a-furacrylato）4（Phen）2（H20）]＇C2HsOH has been synthesized with a-furacrylic acid and 1,10-phenanthroline as the ligands, and its crystal structure was determined. The crystal is of monoclinic system, space group C2/c with a = 1.07388（8）, b = 2.4300（2）, c = 1.86708（14） nm, β= 104.3830（10）°, V= 4.719.4（7） nm3, Dc = 1.503 g/cm3, Z = 2, F（000） = 2196, GOOF = 1.053, the final R = 0.0343 and wR = 0.0883. The crystal structure shows that two neighboring cobalt（II） ions are linked by the bridging coordination of two a-furacrylic acid anions and one water molecule, and their end positions are respectively coordinated with two 1,10-phenanthroline molecules and two a-furacrylic acid anions, forming a dinuclear structure. Both cobalt（II） ions adopt hexa-coordinated distorted octahedral geometry. The electrochemical and fluorescence properties of the title complex are also discussed.
基金Supported by the National Natural Science Foundation of China (20325106 20333070)and the "One-hundred Talent" Project from the Chinese Academy of Sciences
文摘The reaction of anhydrous cobalt(II) dichloride with 1-methylimidazoline-2(3H)- thione in dichloromethane solution gave the title complex, [Co(C4H6N2S)2Cl2]. X-ray single-crystal analysis revealed that the complex crystallizes in a monoclinic system, space group P21/c, a = 13.9707(10), b = 10.0435(7), c = 10.3910(6) ?, β = 91.181(3)o, V = 1457.70(17) ?3, Z = 4, C8H12Cl2N4S2Co, Mr = 358.17, Dc = 1.632 g/cm3, μ = 1.813 mm–1, F(000) = 724, the final R = 0.0710 and wR = 0.1224 for 1549 observed reflections with I > 2σ(I). The Co atom is coordinated by two S atoms from two 1-methylimidazoline-2(3H)-thione ligands and two chloride ions in a slightly distorted tetrahedral geometry. The intramolecular classical hydrogen-bonding interactions involving chloride ions and N–H groups of the heterocyclic thione ligands are observed. The offset π-π stacking interactions between the imidazole rings of adjacent molecules with a face-to-face dis- tance of 3.604 ? are found in the packing diagram.
基金This work was supported by the National Natural Science Foundation of China (No. 20272058) and the Program of Science and Technique Plan of Fujian province
文摘A new polymeric cobalt complex [Co(-male)(py)(H2O)]n (male = maleate; py = pyridine) 1 was prepared by cobalt chloride hexahydrate with disodium maleate and pyridine in an alcohol-aqueous solution. Single-crystal X-ray analysis has revealed that 1 crystallizes in the orthor- hombic system, space group Pnma with a = 18.001(1), b = 7.6001(6), c = 7.4731(6) ? V = 1022.4(1) 3, Z = 4, C9H9CoNO5, Mr = 270.10, Dc = 1.755 g/cm3, F(000) = 548, m(MoK? = 1.683 mm-1, S = 1.002, the final R = 0.0280 and wR = 0.0746 for 883 observed reflections with I > 2s(I). The structure analysis shows an approximate octahedral coordination environment of metal center. The Co(II) ions are bridged by maleic anions in a rare tetradentate coordination fashion with a syn-anti coplanar con- formation of the carboxyl group, forming a two-dimensional corrugated 2-D structure which is further attached into a three-dimensional framework via non-classical CH…O interactions between adjacent layers.
文摘A new cobalt(II) complex, [Co(H2 oxado)3 ]C2 O4 H2 oxado·2H2 O (H2 oxado = oxamide dioxime), has been synthesized in aqueous solution and characterized by elemental analysis and single crystal X-ray structure determination. The complex crystallizes in the triclinic space group P-1, with the parameters a = 9.46(4), b = 11.84(5), c = 12. 81(5)?Å, α = 104.94(6), β = 99.29(5), γ = 106.73(5), V = 1284(9) Å3, Z = 2. The central cobalt(II) cation is pseudo-octahedrally coordinated by six imino N atoms of the neutral oxamide dioxime ligand. In the solid state, each of the following bricks, namely the cationic complexes, the oxalate dianions as well as the oxamide dioxime crystallization molecules, pile up parallel to the a axis. The bulk structure is consolidated by an extended three-dimensional network of hydrogen bridgings—that link the ionic partners, oxamide dioxime and water molecules to one another—and by coulombic interactions.
文摘A new hydrogen bonded Cobalt(II) Schiff base complex,?N’-(pyridine-4-carboxaldehyde) isonicotinoylhydrazone Cobalt(II), has been synthesized from isoniazid and pyridine-4-carboxaldehyde and characterized by IR spectroscopy, 1H-NMR, elemental analysis, TGA and single crystal X-ray structure determination. X-ray crystal structure analysis shows an octahedral complex with a metal centre coordinated to two ligand molecules through the pyridine nitrogen atoms and four water molecules and containing two nitrate groups as counter ions. The complex crystallizes in the monoclinic crystal system and P2(1)/n space group. The unit cell dimensions are: a = 7.2108(4) Å, b = 16.6020(9) Å, c = 13.0389(6) Å,α = 90°, β = 103.972(4)°, γ = 90°. The molecule is symmetrical about the cobalt centre as observed from the 1H-NMR and 13C-NMR and confirmed by the single crystal X-ray structure of the complex. Thermogravimetric analysis shows two steps decomposition of the complex to leave a metal oxide residue. The title compound is expected to be biologically active as one of the precursors (isoniazid) is a therapeutic agent with well-established clinical applications.
文摘A monomeric complex [Co(Im)(2)(O2CMe)(2)] (1) and a novel aqua-bridged dimeric complex 1 [Co-2(mu-H2O)(mu-O2CMe)(2)(Im)(4)(O2CMe)(2)] (2) (Im = imidazole) have been synthesized and characterized. Complexes 1 and 2 coexisted in solution. Pure forms of either complex can be obtained from the same solution by controlling the crystallization conditions. All two complexes possess a carboxylate-Im-cobalt(II) triad system analogous to the carboxylate-histidine-metal triad systems that have been found in many zinc enzymes and cobalt(II)-substituted enzymes. In 2, two Co2+ ions are connected by a water molecule in a bridging fashion with (CoCo)-Co-... [0.3687(1) nm], Co-OH2-[0.2159(3) nm], and Co-OH2-Co [117.2(3)degrees], in which the water molecule is further stabilized by two intramolecular hydrogen bonds with the oxygens of the terminal monodentate acetate groups with the distance of (OO)-O-... [0.2609(7) nm]. The terminal monodentate acetate groups display quite abnormal geometry due to the strong 'pulling effect' on the carboxylates by intermolecular and intramolecular hydrogen bonds. Complex 2 showed weak antiferromagnetic coupling at low temperature with g = 2.22 and J = - 1.60 cm(-1).
基金supported by the National Natural Science Foundation of China(No.20901059and20771083)the Technological Development Foundation Project of Tian jin Educational Committee(No.20080503)
文摘Two one-dimensional cobalt（II） compounds {[Co（Hbpma）（H20）4]2·3SO4·4.5H2O}n 1 and {[Co（Hbpma）（NCS）3（H20）]·2.85H2O}n 2 （bpma = N,N＇-bis（3-pyridylmethyl）amine） have been synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group Pi with a = 15.8780（5）, b = 16.2187（5）, c = 16.4858（5） A, α = 91.0420（10）,β = 94.5190（10）, γ = 101.4360（10）°, V = 4145.7（2） A3, C24H53Co2N6024.5083, Mr = 1031.76, Z = 4, Dc = 1.653 g/cm3, p（MoKa） = 1.046 mm-1, F（000） = 2148, S = 1.017, the final R = 0.0269 and wR = 0.0644 for 13032 observed reflections （I 〉 2a（/））. For complex 2, it belongs to triclinic, space group Pi with a = 9.3761（11）, b = 10.5814（13）, c = 11.2972（14）A, α= 85.472（2）,β = 88.058（2）,γ = 76.203（2）°, V= 1085.0（2） A3, C15Hzl.v0CoN603.85S3, Mr= 502.79, Z = 2, Dc = 1.539 g/cm3, p（MoKa） = 1.112 mm-1, F（000） = 519, S = 1.070, the final R = 0.0358 and wR = 0.0899 for 3466 observed reflections （I 〉 2σ（I））. Two complexes 1 and 2 are both found to be one-dimensional coordination polymers bridged by the protonated bpma ligands, which are assembled into three-dimensional supramolecular structures through the hydrogen bonding interactions and π-π packing interactions.
