Ni(II), Co(II), and Cu(II) complexes incorporating 2-pyrazinecarboxylic acid：Synthesis,characterization, electrochemical evaluation,and catalytic activity for the synthesis of 2H-indazolo[2,1-b]phthalazine-triones

Three complexes containing 2-pyrazinecarboxylate (pzca–), including [Ni(pzca)2(H2O)2], [Co(pzca)2(H2O)2], and [Cu(pzca)2(H2O)2], have been synthesized and characterized using physico-chemical and spectroscopic methods. Furthermore, the structure of each complex was determined by single-crystal X-ray diffraction. All three complexes have an octahedral geometry, where the metal ion chelated by two carboxylate oxygens, two nitrogen atoms belonging to pyrazinic acid molecules, and two oxygen atoms of two water molecules. The catalytic activities of these complex-es were also investigated in the green synthesis of 2H-indazolo[2,1-b]phthalazine-triones by the reaction of hydrazine hydrate with an arylaldehyde, phthalic anhydride, and dimedone in acetic acid.     

2-吡嗪羧酸Ni(II),Co(II)和Cu(II)配合物的合成、表征、电化学测试及其催化合成2H-吲哚[2,1-b]酞嗪三酮（英文）

Three complexes containing 2-pyrazinecarboxylate(pzca–), including [Ni(pzca)2(H2O)2], [Co(pzca)2(H2O)2], and [Cu(pzca)2(H2O)2], have been synthesized and characterized using physicochemical and spectroscopic methods. Furthermore, the structure of each complex was determined by single-crystal X-ray diffraction. All three complexes have an octahedral geometry, where the metal ion chelated by two carboxylate oxygens, two nitrogen atoms belonging to pyrazinic acid molecules, and two oxygen atoms of two water molecules. The catalytic activities of these complexes were also investigated in the green synthesis of 2H-indazolo[2,1-b]phthalazine-triones by the reaction of hydrazine hydrate with an arylaldehyde, phthalic anhydride, and dimedone in acetic acid.     

Synthesis and Structural Characterization of Mono- and Di-nuclear Zinc(Ⅱ) Coordination Compounds of Triphenylphosphoniopropionate

Two novel coordination compounds of Zn(Ⅱ) with Ph3P (CH2)2CO-2(L), namely, [ZnL4(H2O)2]·(ClO4)2·2H2O(compound 1) and [Zn2Cl4(μ-L-O,O′)2](compound 2), have been prepared. The single crystal X-ray structure analysis of these compounds indicates that in compound 1 the Zn(Ⅱ) atom is coordinated by four monodentate carboxylato groups on the equatorial plane and two aqua ligands occupy the axial coordination positions. The pendant oxygen atoms form strong hydrogen bonds with the aqua molecules which results in the stability of this structure. In compound 2, two Zn(Ⅱ) atoms are bridged by a pair of carboxylato groups, showing a skew-bridge mode, and thus enabling a long Zn(Ⅱ)…Zn(Ⅱ) separation. As we know, it is a dinuclear coordination compound with the longest Zn…Zn separation.     

苯四甲酸桥连的镍配合物[Ni(btec)(H2O)4][Ni(imi)2(H2O)4]·2H2O的合成及结构

At room temperature, a coordination polymer [Ni(btec)(H2O)4][Ni(imi)2(H2O)4]·2H2O was synthesized by reaction of NiCl2·6H2O, 1,2,4,5-benzenetetracarboxylic dianhydridc and imidazole in a water/THF solution. The structure was determined by X-ray diffraction crystal structure analysis. It crystallizes in triclinic P1 space group with the crystal cell parameters of a=0.67542 (2) nm, b=1.000 14 (1) nm, c=1.09088 (3) nm, α=74.140(2)°, β= 74.388(1)°, y=73.239(2)°, and V=0.664 09(3) nm3, Z=1. The crystal structure shows that Ni1 atom is coordinated by four water and two imidazole molecules, while Ni2 is coordinated by four water molecules and two carboxyl oxygen atoms. The 1,2,4,5-benzenetetracarboxylate ions bridge Ni2 coordination centers to form one-dimensional chain structure. Moreover, the chains are further linked together by hydrogen bonds to form a two-dimensional network. CCDC: 295873.     

Synthesis and Crystal Structure of a New [Mn_2Ni_2] Cubane Complex

A new Mn2Ni2 cubane complex has been synthesized and characterized by single-crystal X-ray diffraction,FT IR spectra and elemental analysis.The title compound [MnIII2NiII2(hmp)4(N3)4(O2CR)2](hmp-is the anion of 2-pyridinemethanol and O2CR-is α-na-phthaleneacetate)crystallizes in the monoclinic system,space group P21/c with a = 10.519(5),b = 22.109(10),c = 23.235(9),β = 106.096(17)o,C48H42Mn2N16Ni2O8,Mr = 1198.28,V = 5192(4)3,Dc = 1.533 g/cm3,F(000)= 2448,μ = 1.258 cm1,Z = 4,the final R = 0.0875 and wR = 0.2020 for 3398 reflections with I > 2σ(I).X-ray diffraction analysis reveals that each Mn(III)center is octahedrally coordinated by two nitrogen atoms of azide anions and three oxygen atoms from three 2-pyridinemethanol anion ligands together with one oxygen atom from naphthaleneacetate.Each Ni(II)is octahedrally coordinated by two nitrogen atoms of 2-pyridinemethanol anion ligands as well as three oxygen atoms from three 2-pyridinemethanol anion ligands and one oxygen atom from naphthaleneacetate.     

A Three-dimensional Ba(Ⅱ) Coordination Polymer Based on H_4AQTC(Anthraquinone-1,4,5,8-tetracarboxylic Acid): Quinone Oxygen Atoms Participate in Coordination

A novel coordination polymer [Ba2(AQTC)(H2O)3]n(1, H4 AQTC = anthraquinone-1,4,5,8-tetracarboxylic acid) has been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy and thermogravimetric analysis. Two quinone oxygen atoms and all carboxylate oxygen atoms of AQTC4- are involved in coordination. Two equivalent barium ions are mainly linked by carboxylate oxygen atoms into a dimer. Neighbouring dimers are further connected by the AQTC4- ligand through carboxylate oxygen atom, leading to a 1-D chain structure. Every two adjacent chains are mainly further connected by face carboxylate oxygen atoms and water molecule, generating a two-dimensional layer structure. Such 2-D layer structures are connected with O(6) and O(6C) atoms from water molecules to form a 3-D structure. In addition, luminescent properties of 1 are also investigated.     

Synthesis and Structure of Dibenzoyl-bissemicarbazone Neodymium(Ⅲ) Perchlorate

A new Schiff base Dibenzoyl-bissemicarbazone C15H16N6O2(L) and its complex with neodymium(Ⅲ ) perchlorate [NdL2(H2O)2](ClO4)3 were synthesized. The crystal and molecular structure of the title complex were determined by single crystal X-ray diffraction. The crystal is monoclinic and conforms to space group P. with cell constants a=10. 893(2) A, b= 12. 118(3) A , c=22. 494(5) A , β=89. 86(3)% V = 2969.19A3. The final standard deviation R=0. 0919. In the complex Nd is coordinated by four nitrogen and six oxygen atoms, of which four nitrogen and four oxygen atoms are provided by two neutral ligands L, and the other two oxygen atoms are provided by two water molecules, forming a ten-coordinated complex cation, which the perchlorate groups exist in the outer sphere. The coordination polyhedron takes a bicapped anti-square prism arrangement. That the average bond length of Nd-N is 2. 735 A indicates that the coordination of N in groups to Nd( Ⅲ ) is very weak.     

Synthesis and Crystal Structure of a New Dinuclear Manganese(Ⅱ) Manganese(Ⅲ) Complex of a Macrocyclic Ligand

A mixed-valence dinuclear manganese complex, [MnⅡMnⅢL](ClO4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-2-hydroxybenzyl amine, was obtained and its structure was determined by X-ray diffraction. The orange crystal is a monoclinic system with space group P21/c and lattice parameters a=1.1617(4), b=1.4005(3), c=1.4641(3) nm, β=113.03(2)°, and Z=2. The crystal structure shows that each pendant-arm is bonded in a bidentate fashion to the adjacent metal atom and that both the arms are on the same side of the macrocycle. The two Mn atoms are bridged by two μ2-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Mn atom, locating in a trigonal prismatic coordination environment(N3O3), is six-coordinated by the two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from the two oxygen atoms.     

混合价双核锰[Mn2(cyclen)2(μ-O)2](ClO4)3·4H2O的晶体结构和表征

The mixed-valence manganese(Ⅲ/Ⅳ) complex [Mn2(cyclen)2(μ-O)2](ClO4)3-4H2O (1) (cyclen=1,4,7,10-tetraazacyclododecan) with chemical formula C16H48Cl3Mn2N8O18 has been synthesized and characterized by single crystal X-ray diffraction analysis, elemental analysis, IR and electronic spectra. The results showed that the manganese(Ⅲ/Ⅳ) ions were six-coordinated by four nitrogen atoms from cyclen and two oxygen atoms from the oxygen bridge, forming a distorted octahedron geometry. There were two very strong peaks in the range of 400-700 nm in electronic spectrum, which was similar to Mn catalase and Mn ribonucleotide reductase extracted from organisms.Electrochemical study indicated that the complex underwent a quasi-reversible one-electron reduction and oxidation at E1/2=0.827 V in acetonitrile.     

Synthesis and structures of two supramolecular complexes constructed via hydrogen bond linking

Two supramolecular complexes,[Ni(rac-L)]3[CrO4]2[ClO4]2-4H2O (1) and [meso-H2L]0.5[VO3]-0.16H2O (2) (L= 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetra-decane),have been prepared in an aqueous solu-tion,and detected by elemental analysis,IR,TG,and single crystal X-ray diffraction analyses. Com-pound 1 shows a one-dimensional hexagonal prism formed by the hydrogen bonding interactions between the secondary amines of rac-L and CrO42-anion/water molecules. Compound 2 displays a three-dimensional structur...     

SYNTHESIS AND STRUCTURE OF [4Ni(SALEN)·GGH] CLO_4· EtOH·H_2O (GG=Glycylglyciae)

The complex of [4Ni(salen)·GGH] CLO_4·EtOH·H_2O has been synthesized and studied by X-ray single crystal analysis. The results show that there are both intra-unit hydrogen bonds in the [4Ni(salen)·GGH]~+ and inter-unit hydrogen bonds between the two [4Ni(salen)·GGH]~+. Ni(salen) in the unit are still centrosymmetric dimers with planar structure. Imide N(10)—H(10) in the [GGH]~+ bonds with one phenolic oxygen 0(7) of Ni(salen) dimer in the same unit. Two H atoms of amino group N(9)— H [H(A), H(C)] in the glycylglycine perchlorate interact with phenolic oxygen [0(3), 0(5)] of [4Ni(salen)·GGH]~+ through two strong hydrogen bonds respectively.     

Syntheses,Structures and Properties of Two New Coordination Polymers with Flexible Ligands as Linkers

Two new coordination polymers,[ZnL1]_n(1,H_2L1 = 5-(4-pyridyl)-methoxyl isophthalic acid) and[Ni(L2)_2(H_2O)_4]_n(2,HL2 = 4-(pyridin-4-ylmethoxy)benzolic acid),have been synthesized and characterized by elemental analysis,PXRD,IR spectra,and single-crystal X-ray diffraction.Compound 1 has a three-dimensional framework constructed by 6-bridged L1~(2-) anions connecting the Zn_2(O_2C)_4 paddlewheel-like units.Compound 2 contains a mononuclear molecular unit,and the central nickel atom adopts a slightly distorted octahedral geometry by two nitrogen atoms from different L2~- ligands and four oxygen atoms from water molecules.These molecular units link each other via four types of O-H…O hydrogen bonds to form an extended three-dimensional(3D) supramolecular network.The thermal and photoluminescent properties of 1 and 2 have also been investigated.     

Synthesis and Crystal Structure of[Ni(C5H2N2O4)(2, 2'-bipy)(H2O)2]·2H2O

The crystal structure of [Ni(C5H2N2O4)(2, 2?-bipy)(H2O)2]·2H2O 1 has been determined by X-ray diffraction. Crystal data: triclinic system, space group P ī with a = 7.9424(3), b = 9.9417(3), c = 12.1867(3) (A。）, α = 84.771(1), β = 77.375(2), γ = 68.993(2)°, C15H18N4O8Ni, Mr = 440.7, V = 876.16(5) (A。）3, Z = 2, Dc = 1.672 g/cm3, F(000) = 456, ((MoK() = 1.162 mm-1, the final R = 0.0464 and wR = 0.1055 for 3026 observed reflections with I > 2((I). In the title compound, the nickel ion is coordinated by a nitrogen atom and an oxygen atom from the orotate ligand, two nitrogen atoms from 2, 2'-bipy and two oxygen atoms from the coordinated water molecules in a distorted octahedral geometry. The presence of intermolecular hydrogen bonding and (-( stacking interaction of aromatic rings from 2, 2'-bipy results in a 3D structure.     

Crystal Structure and Properties of a Copper(Ⅱ) Complex Containing p-Toluenesulfonate and Imidazole Ligands

A novel supramolecular mixed ligand complex of formula [Cu(PTS)2(Him)2(H2O)2] (C20H26CuN4O8S2,PTS=p-toluenesulfonate,Him=imidazole) has been synthesized in aqueous solution and characterized by elemental analysis,IR and single-crystal X-ray diffraction.The compound crystallizes in the monoclinic system,space group P21/n,Z=2,a=5.650(2),b=14.671(3),c=14.638(3),β=100.10(3)°,V=1194.60(4)3,Dc=1.607 g/cm3,μ(MoKα)=1.143 mm-1,F(000)=598,R=0.0615 and wR=0.1503 for 1752 observed reflections with I 2σ(I).The copper(II) ion in the complex adopts a slightly distorted octahedral coordination geometry and is six-coordinated with N2O4 donor set consisting of two nitrogen atoms and four oxygen atoms provided by the ligands of two imidazole molecules,two water molecules and two p-toluenesulfonate ions.The sulfonate group of the PTS ligand remains weak-coordinated and forms a number of hydrogen bonds with water molecules and imidazole ligands.X-ray structural analysis reveals that the coordination molecules are connected to form a 3-D supramolecular framework by electrostatic interaction,weak van der Waals forces,hydrogen bonding and π-π interaction.The thermal behaviour of the title complex was investigated by using DSC and TG-DTG techniques.     

Structure of Palladium( Ⅱ ) Complex with 2-Hydroxy-propane 1, 3-diamine-N,N,N'''' N'''',-tetraacetic Acid

The reaction of PdCl2 in water with 2-hydroxypropane-1, 3-diaminetetraacetic acid (HPDTA) gave the complex Pd (C11H16N2O9)·1. 5H2O, which was characterized by elemental analysis, IR, NMR and single-crystal X-ray diffraction. The spectroscopic and X-ray diffraction data show that Pd ( Ⅱ ) is coordinated by two nitrogen atoms and two car-boxylic oxygen atoms. The complex crystallizes in monoclinic space group Pc with a = 1. 1240(2), b=1. 1183(2), c=1. 2597(3) nm, β=96. 33(2)°V=1. 5737(6) nm3, Z = 4, R= 0.038. The structure contains two crystallographically independent molecules which have slightly different orientations and are connected by hydrogen bonds.     

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.     

Synthesis,Crystal Structure and Water-induced Reversible Crystal-to-amorphous Transformation Property of [{Ni(IBG)(4,4'-bipy)(H_2O)_2}·3H_2O]_n

A novel NiII complex [{Ni(IBG)(4,4'-bipy)(H2O)2}·3H2O]n 1 (H2IBG = isophthaloylbisglycine and 4,4'-bipy = 4,4'-bipyridine) has been synthesized and characterized by singlecrystal X-ray diffraction, elemental analysis, IR spectra and thermogravimetric analysis. It crystallizes in monoclinic, space group P2/c with a = 15.5420(7), b = 22.4344(1), c = 8.3455(5), β = 101.538(3)o, V = 2670.1(7)3, Z = 4, C22H32N4NiO13, Mr = 619.23, Dc = 1.443 g/cm3, F(000) = 1296.0, μ(MoKα) = 0.750 mm-1, the final R = 0.0570 and wR = 0.1445 for 2296 observed reflections with I 2σ(I). In the structure, the NiII metal center is coordinated in an octahedral environment arranged by two water molecules, two carboxylate oxygen atoms and two nitrogen atoms from two 4,4'-bipy ligands. Thermal decomposition and powder X-ray diffraction results indicate that the transformation from the crystal form, [{Ni(IBG)(4,4'-bipy)(H2O)2}·3H2O]n, to the amorphous powder, Ni(IBG)(4,4'-bipy)(H2O)2, is reversible, so the latter form may be utilized as an absorbing agent for water and water vapor.     

Three New Polyoxometalates Derivatives Decorated by Phenanthroline and Transition-metal Cations(M=Zn~ⅡI,Co~Ⅱ , Ni~Ⅱ)

Three new Keggin polyoxometalates, [Zn(phen) 3 ] 2 [SiW 12 O 40 ]·5H 2 O(1), [Co(phen) 3 ] 2 [SiW 12 O 40 ](2) and [Ni(phen) 3 ] 2 [SiW 12 O 40 ]·2H 2 O(3)(phen=1,10′-phenanthroline) have been hydrothermally synthesized and characterized by elemental analysis, IR, crystal X-ray diffraction, thermogravimetric analyses(TGA) and fluorescence techniques. Complex 1, crystallized in the triclinic space group P1, consists of one [SiW 12 O 40 ] 4– anion, two discrete [Zn(phen) 3 ] 2+ cations and five crystal water molecules. Complexes 2 and 3 have the similar configuration to complex 1, but they crystallized in the monoclinic space group C2/c. Variable-temperature magnetic susceptibilities of complexess 2 and 3 reveal antiferromagnetism and ferromagnetism, respectively.     

Cyanide-bridged complexes based on dinuclear Cu(II)-M(II) [M = Pb and Cu] building blocks: Synthesis, crystal structures and magnetic properties

Four cyanide-bridged heterometallic complexes {[CuPb(L 1 )][Fe III (bpb)(CN) 2 ]} 2 ·(ClO 4 ) 2 ·2H 2 O·2CH 3 CN (1), {[CuPb(L 1 )] 2 [Fe II (CN) 6 ](H 2 O) 2 }·10H 2 O (2), {[Cu 2 (L 2 )][Fe III (bpb)(CN) 2 ] 2 }·2H 2 O·2CH 3 OH (3) and {[Cu 2 (L 2 )] 3 [Fe III (CN) 6 ] 2 (H 2 O) 2 }·10H 2 O (4) have been synthesized by treating K[Fe III (bpb)(CN) 2 ] [bpb 2-=1,2-bis(pyridine-2-carboxamido)benzenate] and K 3 [Fe III (CN)] 6 with dinuclear compartmental macrocyclic Schiff-base complexes [CuPb(L 1 )] (ClO 4 ) 2 or [Cu 2 (L 2 )]·(ClO 4 ) 2 , in which H 2 L 1 was derived from 2,6-diformyl-4-methyl-phenol, ethylenediamine, and diethylenetriamine in the molar ratio of 2:1:1 and H 2 L 2 from 2,6-diformyl-4-methyl-phenol and propylenediamine in the molar ratio of 1:1. Single crystal X-ray diffraction analysis reveals that compound 1 displays a cyclic hexanuclear heterotrimetallic molecular structure with alternating [FeⅢ (bpb)(CN) 2 ]- and [CuPb(L 1 )] 2+ units. Complex 2 is of a neutral dumb-bell-type pentanuclear molecular configuration consisting of one [Fe(CN)6] 4- anion sandwiched in two [CuPu(L 1 )] 2+ cations, and the pentanuclear moieties are further connected by the hydrogen bonding to give a 2D supramolecular framework. Heterobimetallic complex 3 is a tetranuclear molecule composed of a centrosymmetric [Cu 2 (L2)] 2+ segment and two terminal cyanide-containing blocks [FeⅢ (bpb)(CN)2 ]- . Octanuclear compound 4 is built from two [Fe(CN)6]3- anions sandwiched in the three [Cu 2 L 2 ] 2+ cations. Investigation of their magnetic properties reveals the overall antiferromagnetic behavior in the series of complexes except 2.     

Synthesis and Crystal Structure of 3,3＇-Bis（2-benzimidazolyl）-2,2＇-dipyridine with Hydrated Zinc（Ⅱ） Perchlorate

The reaction of Zn(ClO4)2·6H2O with 3,3'-bis(2-benzimidazolyl)-2,2'-dipyridine (L) gave a mononuclear zinc(II) complex: [ZnL2](ClO4)2·2DMF·4H2O, which was structurally characterized by EA, IR, UV, 1H NMR, fluorescence spectrum and single-crystal X-ray diffraction. The crystal (C54H54Cl2N14O14Zn, Mr = 1259.38) belongs to the monoclinic system, space group C2/c with a = 20.874(2), b = 14.9953(16), c = 20.462(3) , β = 101.553(2)°, V = 6274.8(13) 3, Z = 4, Dc = 1.333 g/cm3, F (000) = 2608, μ(MoKα) = 0.548 mm–1, R = 0.0682 and wR = 0.1931 for 4984 observed reflections with I > 2σ(I). The Zn(II) is four-coordinated in a slightly distorted tetrahedral geometry through four N atoms from four benzimidazole units of two ligands. In the crystal lattice, the [ZnL2]2+ cations are linked to each other by extensive intermolecular hydrogen bonds between nitrogen atoms of benzimidazole rings, water and DMF molecules.