Syntheses and Crystal Structures of Cd(Ⅱ) and Ni(Ⅱ) Complexes Containing Flexible Sulfide and Nitrogen Heterocyclic Ligands

Two new coordination polymers [Cd(EBLA)(ip)(H2O)](1) and [Ni(EBSA)(im)2(H2O)]n(2) were synthesized by hydrothermal and solution methods using 2,2'-dithiosalicylicacid(EBSA), 1H-imidazo[4,5-f][1,10]phenanthroline(ip), imidazole(im), Cd(NO3)2·4H2O and Ni(NO3)2·6H2O. The complexes were characterized by elemental analysis and FT-IR. Meanwhile, the crystal structures, fluorescence properties of complex 1 and thermogravimetrie analysis of complex 2 have been studied. In complex 1, 2,2'-dicarboxydiphenylthioether(EBLA) was prepared with 2,2'-dithiosalicylicacid(EBSA) in situ reaction by hydrothermal method. Complex 1 is a dinuclear structure and Cd2+ is five-coordinated in a distorted trigonal bipyramidal geometry. Complex 2 is a one-dimensional infinite linear chain and Ni2+ is six-coordinated to form a distorted octahedral geometry. Hydrogen bonding and π-π interactions are observed in these complexes.     

The structural characterization of some palladium (Ⅱ) complexes of 1,10-phenanthroline and amino acids by NMR spectroscopy

The complexes [Pd(phen)(aa)]Cl.3H2O, where phen is 1,10-phenanthroline and aa is the anion of glycine (gly), .DL-alanine (ala), DL-serine (ser) or DL-asparagine (asn), were synthesized and characterized by spectroscopies. The NMR signals were assigned completely on the basis of the double irradiation, 1H-1H COSY and 1H-13C COSY techniques. In the 1H NMR spectra of phen in the complexes, the signals of 2-H and 9-H show upfield shifts 0.8-1 ppm, while the signals of 4-H and 3-H show downfield shifts or almost no shift, as compared to the free phen ligand, and the signal of 4-H appears in the lowest field. The signals of ring B which is trans to the carboxyl group show significant upfield shifts as compared to those of ring A. The probable structures were described on the basis of a metal-non-bonded hydrogen interaction, trons effect and ligand-ligand interaction. There may exist three conformation isomers in the [Pd(phen)(asn)]Cl.3H2O complex at room temperature. The preferred conformation isomer is about     

Two New Mn(Ⅱ)/Co(Ⅱ) Complexes Assembled by 2,5-Dihydroxy-1,4-benzenedicarboxylic Acid and Phenanthroline or Derivative

Two new complexes [Mn(DHTA)(PLQ)]n(1) and{[Co2(DHTA)(phen)2(H2 O)6]· DHTA}n(2)(H2 DHTA = 2,5-dihydroxy-1,4-benzenedicarboxylic acid, PLQ = 1,10-phenanthroline-5,6-quinone, phen = 1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, fluorescence spectrum, single-crystal and power X-ray diffraction. Complex 1 exhibits a two-dimensional(2 D) network, which was stabilized through O–H···O hydrogen bonding interactions. Complex 2 shows a zero-dimensional structure, which was further extended into a three-dimensional supramolecular structure through O–H···O hydrogen bonds and π-π interactions.     

Two New Copper(Ⅱ) Complexes with p-Cyanobenzoic Acid: Synthesis,Crystal Structures and Properties

The complexes of [Cu(bpy)(H2O)(CBA)2]n 1 and [Cu(phen)(H2O)(CBA)2]·H2O 2 based on p-cyanobenzoic acid(HCBA) have been synthesized in aqueous ethanolic solution at room temperature. The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in orthorhombic and complex 2 is of triclinic system. The results indicate the complex 1 shows a 1D chain structure bridged by two carboxylic oxygen atoms from CBA–, and complex 2 is a mononuclear structure. Through intermolecular hydrogen bonding and π...π stacking interactions, the complexes are assembled into supramolecular structures. Complex 1 has been characterized by magnetic measurements. The magnetic measurement indicates that weak ferromagnetic interaction(zJ= 0.038(5)) between the Cu2+ ions is dominant in the structure. The IR spectrum and results of thermal and elemental analyses are also presented.     

Syntheses,Crystal Structures and Magnetic Properties of Ni(Ⅱ) and Mn(Ⅱ) Coordination Polymers Constructed from 5-(2'-Carboxylphenyl) Nicotate and 2,2'-Biimidazole

Two coordination polymers, namely {[Ni(cpna)(H2biim)(H2O)]·H2O}n(1) and {[Mn(cpna)(H2biim)]·H2O}n(2)(H2cpna = 5-(2'-carboxylphenyl) nicotic acid, H2biim = 2,2'-biimidazole),have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. Compound 1 exhibits a one- dimensional(1D) step-like chain structure, which further builds a three-dimensional(3D) supramolecular architecture via O–H···O and N–H···O hydrogen-bonding and π-π stacking interactions. Compound 2 possesses a one-dimensional(1D) double chain structure, which is further assembled into a 3D supramolecular framework by N–H···O hydrogen bonding and π-π stacking interactions. Magnetic susceptibility measurement indicates that compound 1 shows a weak antiferromagnetic coupling between the nearest Ni(II) centers, with g = 2.11 and J = –1.87 cm–1.     

Hydrothermal Syntheses,Crystal Structures,and Characterization of Two Zinc(Ⅱ) Complexes Containing Flexible Bis(benzimidazole) Ligands

Two zinc(Ⅱ) complexes, namely, [Zn(L_1)Cl_2]_2(1) and {[Zn(L_2)(tbta)]·3H_2O}n(2)(L_1 = 1,3-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2 tbta = tetrabromoterephthalic acid, L2_ = 1,3-bis(2-methylbenzimidazol-1-yl)-2-propanol), have been successfully obtained under hydrothermal conditions. Complex 1 displays a binuclear structure which is further extended into a 1D supramolecular chain through π-π stacking. Complex 2 features a 2D(4,4) network based on a L2/tbta2- double linker. The thermal stability, fluorescence properties and catalytic activities of two complexes for the degradation of methyl orange in a Fenton-like process were discussed.     

Syntheses,Crystal Structures and Magnetic Properties of Two New Low-dimensional Manganese (Ⅱ) Coordination Compounds

Two new low-dimensional Mn(Ⅱ) coordination compounds of Mn(H_2pimdc)_2(phen)(compound 1) and [Mn(Hpimdc)(phen)]n·nH_2O(compound 2) were synthesized, where H_3pimdc is a 2-propyl-imidazole-4,5-dicarboxylic acid and phen is 1,10-phenanthroline. Both compounds were thoroughly analyzed by X-ray single-crystal diffraction, element analysis, IR spectra, PXRD and thermal analysis. X-ray single-crystal diffraction analyses indicate that the phen ligands terminate metal ions on two sides to prevent the linkage between the neighboring metal ions into a higher dimensional structure in compounds 1 and 2. Compound 1 is constructed from mononuclear molecules which form the 1D helical supramolecular chain by N–H···O hydrogen bonds. In compound 2, Hpimdc is a tetradentate bridging ligand, which binds Mn(Ⅱ) ions to generate a single-stranded right helical chain parallel to the b axis. These 1D chains are additionally coupled by H-bonds as well as π···π stacking interactions, which formed a 3D supramolecular structure. Additionally, compound 2 demonstrated temperature-dependent magnetic susceptibility and negative value of θ(equal to –9.09 K), which is indicative of weak antiferromagnetic interactions between Mn(Ⅱ) ions.     

Syntheses,Crystal Structures and Luminescent Properties of Lead(Ⅱ) and Cadmium(Ⅱ) Coordination Polymers Constructed from Biphenyl-2,5,3′-tricarboxylate

Two coordination polymers, namely [Pb(Hbtc)(phen)]n(1) and {[Cd3(btc)2(H2O)4]·2H2O}n(2, H3btc = biphenyl-2,5,3'-tricarboxylic acid, phen = 1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a zigzag chain 1D coordination network, which is further extended into a 3D supramolecular architecture via O–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 3D open framework based on a tricadmium(II) subunit, generating a trinodal 4,4,6-connected net with the 4,4,6T24 topology defined by the point symbol of(44·62)3(46·69)2. Thermal stability and luminescent properties of both compounds were studied and discussed.     

Synthesis, crystal structures and fluorescence properties of four mixed-ligands Zn(Ⅱ) and Cd(Ⅱ) coordination compounds

Four new coordination compounds, [Zn(dba)(bpy)]n (1), {[Zn(dba)(phen)]·2H2O}n (2), [Cd(dba)(bpy)(H2O)2] (3) and [Cd2(dba)2(phen)2]n (4) (H2dba = 2,5-dihydroxy-p-benzenediacetic acid, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) have been prepared via solvothermal method and characterized by sin-gle-crystal X-ray diffraction, infrared spectroscopy, elemental analysis and powder X-ray diffraction. 1 and 2 possess 1D infinite chain structures. Complex 3 exhibits a mononuclear structure. Complex 4 owns bi...     

Substituent groups from aromatic dicarboxylates modulated structural diversification in the assembly of Co(II) complexes based on the bis-pyridyl-bis-amide ligands

Four coordination polymers based on two bis-pyridyl-bis-amide ligands and three aromatic dicarboxylates with different substituent groups, namely, [Co(3-bpcb) 1.5 (NPH)(H2O)]·4H2O (1), [Co(3-bpcb)(NIPH)] (2), [Co(3-bpcb)0.5 (5-H2 AIP)]·2H2O (3), [Co(3-bpcd) 0.5 (5-H2 AIP)(H2O)]·2H2O (4) [3-bpcb = N,N′-bis(3-pyridinecarboxamide)-1,4-benzene, 3-bpcd = N,N′-bis(3- pyridine)cyclohexane-1,4-dicarboxamide, H2 NPH = 3-nitrophthalic acid, H2 NIPH = 5-nitroisophthalic acid, 5-H4 AIP = 5-aminoisophthalic acid] have been synthetized under hydrothermal conditions. Complex 1 displays a one dimensional (1D) chain based on the binuclear [Co2 (NPH)2 ] units and 3-bpcb ligands, which is extended into a three dimensional (3D) supramolecular framework through hydrogen bonding and - stacking interactions. In complex 2, the (3,5)-connected two dimensional (2D) layers are constructed from 1D Co-NIPH chains and bidentate-bridging 3-bpcb ligands. Complex 3 is a 2D double layer based on Co-5-H2 AIP 2D layers and 3-bpcb pillars. Complex 4 also displays a 2D network, which is constructed from the Co-5-H2AIP 1D double chains and 3-bpcd ligands. Finally, complexes 2-4 are extended into 3D supramolecular frameworks by hydrogen bonding or - stacking interactions. The substituent groups of dicarboxylates play an important role in the assembly and structures of the title complexes. In addition, the fluorescent properties of complexes 1-4 and the electrochemical behaviors of 3 and 4 at room temperature have been investigated.     

Two Zinc(Ⅱ) Complexes Based on 7rany-(1R,2R)-cyclohexanediamine: Molecular Structure Analyses and Preparation of Composite Membrane

Two novel complexes Zn2(chda)2(TPA)Cl2(1) and [Zn(chda)2(H2O)2](TPAXH2O)2(2)[chda is a chiral ligand of trans-(1R,2R)-cyclohexanediamine, H2TPA is terephthalic acid] were synthesized at room temperature. The molecular structures of complexes 1 and 2 were identified by single-crystal X-ray diffraction measurement. The results showed that complex 1 had a binuclear structure, each Zn(Ⅱ) ion was four coordinated by two N atoms of chda, one O atom of TPA and one Cl atom, to construct a distorted tetrahedral geometry. For complex 2, the Zn(Ⅱ) ion was six coordinated by two chda molecules and two water molecules to form a ZnN4O2 octahedral geometry. Complexes 1 and 2 further extended into three-dimensional supramolecular frameworks by hydrogen-bonding interactions. Hirshfeld surface analysis and fingerprint plots were used to further analyze the contribution of diflerent intermolecular interactions. Further, a composite membrane [Zn(chda)2(H2O)2](TPA)(H2O)2/CA was prepared by adding 10%(mass fraction) of complex 2 into cellulose acetate using acetone/chloroform( V:V-1:1) as solvent.     

Two Zinc Architectures: A Mononuclear Complex and a 2D Wave-like Organic-inorganic Hybrid Layer

Self-assembly of Zn(NO3)2·6H2O and 2,3,5,6-tetrabromoterephthalic acid(H2TBTA) gave rise to two new zinc metal-organic frameworks,Zn(HTBTA)2(phen)2·H2O(1) and Zn(TBTA)1/2(μ2-OH)(H2O)·0.25EtOH(2).Complex 1 is a mononuclear molecule.The hydrogen bonding interactions further connect the mononuclear molecules to generate a 2D supramolecular architecture.Complex 2 is a 2D organic-inorganic hybrid layer framework constructed from 1D rod-shaped secondary building units.     

Syntheses and Characterizations of Two Manganese(Ⅱ) Coordination Polymers Containing Three-dimensional Interpenetrating Networks Constructed by Mixed Ligands

Two new three-dimensional coordination polymers, namely [Mn(L)(bpdc)]n(1), [Mn(L)0.5(ndc)]n(2)(L = 1,4-bis(2-methylbenzimidazole)butane, H2 bpdc = 4,4?-biphenyldicarboxylic acid, H2 ndc = 2,6-naphthalenedicarboxylic acid) have been successfully synthesized under hydrothermal conditions. Two complexes were characterized by physico-chemical, spectroscopic methods and single-crystal X-ray diffraction. Complex 1 shows a 3D → 3D 5-fold interpenetrated network with a 4-connected uninodal dia topology. Complex 2 possesses a 3D → 3D 3-fold interpenetrating architecture with a binodal(4,5)-connected xah topology. The fluorescence and thermal properties of the title complexes were discussed.     

Temperature-dependent Syntheses of Two Manganese(Ⅱ) Coordination Compounds Based on an Ether-bridged Tetracarbolylic Acid

0D dinuclear manganese(Ⅱ) coordination compound and 1 D chain manganese(Ⅱ) coordination polymer, namely [Mn_2(μ-L)(phen)4]·4 H_2 O(1) and {[Mn_2(μ5-L)(phen)_2]·H_2O}n(2), have been constructed hydrothermally using H4 L(H4 L = 2,3,3',4'-diphenyl ether tetracarboxylic acid), phen(phen = 1,10-phenanthroline), and manganese chloride at 120 and 160℃, respectively. 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. Single-crystal X-ray diffraction analyses revealed that two compounds crystallize in the triclinic or monoclinic system, space group P1 or P2_1/c. Compound 1 discloses a discrete dimeric structure, which is assembled into a 3 D supramolecular framework through O–H···O hydrogen bond. Compound 2 has a chain structure. Structural differences between compounds 1 and 2 are attributed to the different reaction temperature. Magnetic studies for compound 2 demonstrate an antiferromagnetic coupling between the adjacent Mn(Ⅱ) centers.     

Syntheses,Crystal Structures,and Magnetic Properties of Mn(Ⅱ) and Co(Ⅱ) Coordination Polymers Constructed from Pyridine-tricarboxylate Ligand

Two coordination polymers, namely {[Mn(HL_1)(phen)]·4H_2O}_n(1) and [Co_2(HL_2)_2(H_2O)_2]_n(2) have been constructed hydrothermally using H_3L_1 and H_3L_2(H_3L_1 = 2-(5-carboxypyridin-2-yl)terephthalic acid, H_3L_2 = 2-(4-carboxypyridin-3-yl)terephthalic acid), phen, MnCl_2×4H_2O and CoCl_2×6H_2O. The products were isolated as stable crystalline solids and were characterized by IR spectroscopy, elemental, thermogravimetric(TGA), powder(PXRD) and single-crystal X-ray diffraction analyses. Compound 1 features a 3D framework structure, which was topologically classified as a trinodal 4,6,6-connected net with the unique topology defined by the point symbol of(3~(10).5.6~4)4(3~(10).6.7~4)2(5.6~2.8~2.9). Compound 2 possesses a 2D metal-organic layer, which was topologically classified as a binodal 4,4-connected layer defined by the point symbol of(4~3.6~2.8). The layers are further extended into a 3D supramolecular framework via hydrogen bonds. The magnetic properties for both compounds were also investigated, indicating antiferromagnetic interactions between the adjacent metal ions.     

Synthesis,Crystal Structure and Antitumor Activity of a Na(Ⅰ) Coordination Polymer Based on 2-Propyl-4,5-imidazoledicarboxylic Acid and 1,10-Phenanthroline Ligands

A new Na(I) coordination polymer, [Na2(Hpimdc)(H2 pimdc)(phen)2]n(1), has been synthesized by the reaction of NaOH with 2-propyl-4,5-imidazoledicarboxylic acid(H3 pimdc)and 1,10-phenanthroline(phen). The Na(I) coordination polymer 1 was characterized by single-crystal X-ray diffraction analysis and elemental analysis. In 1, the bridged ligand H3 pimdc adopts two modes(singly deprotonated and doubly deprotonated) to coordinate with the Na(I) ion.The Na(1) ion is six-coordinated with three N atoms from a phen ligand and a H2 pimdc ligand,three O atoms from a Hpimdc ligand and two other different H2 pimdc ligands. The Na(2) ion is also six-coordinated with three N atoms from a phen ligand and a Hpimdc ligand, three O atoms from a H2 pimdc ligand and other two different Hpimdc ligands. Complex 1 exhibits a 1 D chain structure built up by μ-H2 pimdc-and μ-Hpimdc2-ligands. The antitumor activities of complex 1 against human SGC7901, A549 and H08910 cells have been tested.     

Syntheses,Crystal Structures and Properties of Co（Ⅱ） and Cu（Ⅱ） Complexes with 5-Nitro-1,2,3-benzenetricarboxylic Acid

Two new coordination polymers,{[Co(O2N-Hbtb)(phen)(H2O)3]·2H2O}n 1 and {[Cu3(O2N-btb)2(bipy)2(H2O)4]·4H2O}n 2(O2N-H3btb=5-nitro-1,2,3-benzenetricarboxylic acid,phen=1,10-phenanthroline,bipy=2,2'-bipyridine),were prepared through hydrothermal reactions of Co(Ⅱ) or Cu(Ⅱ) salt with O2N-H3btb in the presence of different auxiliary N-donor ligands.Their crystal structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis and IR spectroscopy.In the two complexes,O2N-H3btb ligand acts as monodentate and bis-monodentate modes,respectively.Complex 1 displays a two-dimensional layered structure through the inter-and intramolecular hydrogen bonding interactions while complex 2 has an O2N-btb bridged one-dimensional chain which is extended into a three-dimensional network by hydrogen bonding interactions.The magnetic properties of complex 2 are investigated over the temperature range of 2～300 K and ferromagnetic interactions are observed.     

Synthesis,crystal structures and spectral properties of cobalt (Ⅱ) complexes:[ CoL (N_3) ] ·ClO_4 and CoL (N_3)_2 [L=tris ((3,5-dimethylpyrazol-1-yl) methyl) amine

Two monomeric cobalt(Ⅱ)complexes,[CoL(N3)] ClO4(1)and CoL(N3)2(2),where L is tris((3,5-dimethylpyrazol-1-yl)methyl)amine,were synthesized and their crystal structures were determined by X-ray diffraction technique.Complex 1 is five coordinated with one azide nitrogen atom and four nitrogen atoms of the tris((3,5-dimethylpyrazol-l-yl)-methyl)amine ligand,and the metal center is in distorted trigonal bipyramidal environment.Complex 2 is six coordinated distorted octahedron with the two azide nitrogen atoms and four nitrogen donors of the tris((3,5-dimethylpyrazol-1-yl)-methyl)amine ligand.The solution behaviors of the title complexes have been further investigated by UV-Vis,and 1H NMR analysis.It is found that the formation of 1 and 2 depends on the molar ratio of the azide ion to metal salt and ligand Complex 1 attached with one azide group is more stable and easy to generate than complex 2 incorporated with two azide groups,and the reasons were well discussed.     

Synthesis and Properties of u-Oxamido Heterobinuclear Cu(Ⅱ)-Co(Ⅱ) Complexes

Three heterobinuclear complexes were synthesized, namely [Cu (oxpn) Co (L)2] (ClO4)2·xH2O(L= 2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen) , and 5-nitro-1, 10-phenanthroline (NO2-phen)), where oxpn represents N, N'-bis(3-aminopropyl) oxam-ido. Based on 1R, elemental analysis, conductivity measurement and electronic spectra, these complexes were characterized by an extended oxamido-bridged structure with Cu(Ⅱ) in a planar environment and Co(Ⅱ) in a octahedral environment. The symmetry of the cation is very close to C2v.The complexes were also characterized with variable temperature (4~300K) magnetic susceptibility, and the data were fit for the susceptibility equation derived from spin Hamilton, H= -2JS1.S2-DSx12 by least square strategy. The exchange integral, J, was found to be -22.36 cm-1 (for bpy);-15.45 cm-1 (for phen); -19. 10cm-1(for NO2-phen), indicating that there is a weak antiferromagnetic spin-exchange interaction between the metal ions.     

Syntheses,Crystal Structures and Catalytic Properties of Copper(Ⅱ) and Cobalt(Ⅱ) Complexes Containing 5,6-Dimethylbenzimidazole

Two new complexes, [Cu(DMB)2(NAA)2](1) and [Co(DMB)2(NAA)2](2)(DMB = 5,6-dimethylbenzimidazole, HNNA = 1-naphthylacetic acid), were hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, TGA, PXRD and single-crystal X-ray diffraction analysis. The coordination geometry of the metal centers is a perfect square plane for 1 and a distorted tetrahedron for 2. In compound 1, the mononuclear units are linked by N–H···O hydrogen bonds to form a 1D chain structure, while mononuclear motifs of 2 are extended via N–H···O hydrogen bonding and π-π stacking interactions into a 2D supramolecular layer. The remarkable catalytic properties of the two complexes for the degradation of Congo red dye have been found.