Synthesis,Crystal Structure and Cytotoxic Activity of a Zinc(Ⅱ) Complex of the Schiff Base Derived from S-benzyldithiocarbazate

A novel zinc（Ⅱ） complex of empirical formula,ZnL2（L=anionic forms of S-benzyl-β-N-（2,4-dichlorobenzylidene） hydrazine carbodithioate）,has been synthesized and characterized by elemental analysis,IR spectra and single-crystal X-ray diffraction.The crystal belongs to the triclinic system,space group P with a = 9.3168（9）,b = 13.0353（13）,c = 14.7702（15） ,α = 71.2860（10）,= 87.5140（10）,γ = 79.4480（10）o,V = 1670.0（3） 3,Z = 2,Mr = 773.93,Dc = 1.539 g/cm3,μ = 1.334 mm-1,F（000） = 784,the final R = 0.0403 and wR = 0.0800 for 4060 observed reflections with I〉2（I）.In the crystal structure,the zinc（Ⅱ） complex has a distorted tetrahedral geometry in which the zinc ion is coordinated by the nitrogen and sulfur atoms from two Schiff base ligands,respectively.The preliminary bioassay indicates that the Schiff base and its zinc complex exhibit inhibitory activity against the human gastric cancer cell lines（MKN45） and hepatoma cell lines（HepG2）.

Synthesis and Crystal Structure of a Novel Dinuclear Copper(Ⅱ) Complex Containing Benzimidazole Schiff Base Ligand

A novel dinuclear copper（Ⅱ） complex [CuL（NO3）]2·2MeOH was obtained by the coordination reaction of Cu（NO3）2·3H2O with ligand HL （HL=N-（methyl-2-benzimidazol- methylidene）-2-hydroxyaniline）. The single-crystal X-ray analysis has revealed that the complex crystallizes in triclinic, space group P with a=9.535（3）, b=10.009（3）, c=10.666（4） , α=104.303（4）, β=100.105（4）, γ=115.917（4）o, V=839.0（5） 3, C16H16CuN4O5, Mr=407.87, Z=2, Dc=1.614 g/cm3, F（000）=418, μ=1.338 mm-1, R=0.0543 and wR=0.0980. The basic dinuclear copper（Ⅱ） complex units [CuL（NO3）]2 are formed by NO3- as co-bridging ligands and L as NNO tridentate chelate coordinating to the copper ions. The ladder-like one-dimensional chain motifs are formed by O…H-O and O…H-N hydrogen bonds from methanol molecules connecting the dinuclear copper（Ⅱ） units.

Syntheses, Crystal Structures and Antibacterial Activities of Cobalt(Ⅱ) and Manganese(Ⅱ) Complexes with Schiff Base Ligand Derived from Tryptamine

Two new mononuclear complexes, namely [Co（L）2]（1） and [Mn（L）2]（2）（HL = N-（3-methylsalicylidene）tryptamine）, have been synthesized by the reactions of the ligand with cobalt acetate or manganese acetate in anhydrous ethanol. The crystal structures of the complexes were characterized by IR spectrum, elemental analysis, PXRD and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group C2/c, with a = 23.146（2）, b = 9.4864（10）, c = 13.9261（15）A, β = 102.898（2）°, V = 2980.6（5） ？3, Z = 4, Dc = 1.367 g/cm3, F（000） = 1284 and μ = 0.616 mm^-1. Complex 2 crystallizes in monoclinic, space group P21/n, with a = 14.807（11）, b = 13.118（10）, c = 16.663（13） A, β = 111.237（14）°, V = 3017（4） A^3, Z = 4, Dc = 1.342 g/cm^3, F（000） = 1276 and μ = 0.477 mm-1. The units of complex 1 are linked by intermolecular N–H…π hydrogen bonds into infinite 1D chains, which are further extended into a 3D supramolecular structure by a series of π···π stacking interactions. The units of complex 2 are linked by intermolecular N–H…π hydrogen bonds and C–H…π hydrogen bonds into an infinite 3D supramolecular structure. Meanwhile, the antibacterial activities of the ligand and its complexes have been tested against four kinds of bacteria. The results show that the three compounds all have excellent antibacterial activities and that 1 and 2 possess stronger inhibiting effects against the bacteria than the Schiff base.

Synthesis and Crystal Structure of a Zinc(II) Complex Salt with the Schiff Base of Picolinaldehyde N-oxide and Semicarbazone

The title zinc（Ⅱ） complex salt [Zn（H2O）6]（ClO4）2-（PNOS）4, where PNOS is derived from picolinaldehyde N-oxide with semicarbazone, has been prepared and structurally characterized by X-ray single-crystal analysis. It crystallizes in triclinic, space group PI with a = 7.529（3）, b = 10.206（4）, c = 14.678（6）A, a = 86.293（6）, β= 87.686（7）, γ= 81.382（6）°, C28H44Cl2N16O22Zn, Mr = 1093.06, V = 1112.3（8） ,A^3 Z = 1, Dc = 1.632 g/cm^3, S = 1.089, μ（MoKa） = 0.773 mm^-1, F（000） = 564, the final R = 0.0438 and wR = 0.1076 for 3888 independent reflections with Rint = 0.0224. The crystal structure possesses a [Zn（H2O）6]^2＋ cation, two ClO4^- anions and four PNOSs. In the crystal structure, Zn^2＋ cation is located at the symcenter and coordinated by six water molecules. In [Zn（H2O）6]^2＋, an elongate octahedral complex cation, the average Zn-O bond length is 2.087（2） A. There exist a lot of H bonds in the structure, linking the cation [Zn（H2O）6]^2＋, anion ClO4^- and PNOS to form a 3D network.

Syntheses, Characterizations, Crystal Structures and Antibacterial Activities of Two Zinc(II) Complexes with a Schiff Base Derived from o-Vanillin and p-Toluidine

Two new zinc（Ⅱ） complexes, [Zn2L2Ch].2[ZnL（CH3OH）Cl2] 1 and [ZnL2（NO3）2] 2, were synthesized by reacting ZnX2.nH2O （X = Cl^-, NO3^-） and a Schiff base ligand 2-[（4-methylphenylimino）methyl]-6-methoxyphenol （C15HIsNO2, L） which was obtained by the condensation of o-vanillin （2-hydroxy-3-methoxybenzaldehyde） with p-toluidine. Both 1 and 2 were characterized by single-crystal X-ray diffraction technique, elemental analysis, molar conductance, FT-IR, UV-Vis, IH-NMR spectra and thermogravimetrie analysis. The Schiff base ligand and its zinc（Ⅱ） complexes have been tested in vitro to evaluate their antibacterial activity against bacteria, viz., Escherichia Coli, Staphylococcus aureus and Bacillus Subtilis. The results show that these complexes have higher activity than the corresponding free Schiff base ligand against the same bacteria.

Synthesis and Crystal Structure of a Co(II) Complex with Schiff Base and Imidazole Ligand

The title compound, [Co（C3H4N2）2（C22H18N2O4）]·5H2O （Mr = 659.56）, has been prepared and its crystal structure was determined by X-ray diffraction method. The crystal belongs to monoclinic, space group P21/n, a = 9.6808（2）, b = 26.7204（5）, c = 12.7993（3） A, β = 100.9340（10）°, V= 3250.75（12） A^3, Z = 4, Dc = 1.348 g/cm^3,μ = 0.586 mm^-1, F（000） = 1380, S = 1.131, R = 0.0689 and wR = 0.1883 for 4782 observed reflections （Ⅰ 〉 2σ（Ⅰ））. The title crystal consists of Co（Ⅱ） complex and lattice water molecules. The Co（Ⅱ） complex assumes a distorted octahedral coordination geometry, formed by one Schiff base dianion phenylenediamine-3-methoxysali-cylaldehyde and two imidazole ligands. The π-π stacking interaction occurs between nearly parallel benzene rings of the neighboring complexes.

Novel Isatin-Schiff Base Cu (II) and Ni(II) Complexes. X-ray Crystal Structure of Bis[3-(4-hexylphenylimino)-1H-indol-2(3H)-one]-dichlorocopper(II) Complex

Schiff base ligand （HL） derived from 4-hexylaniline with isatin （1H-indole-2,3-dione） and its complexes with Cu（Ⅱ）, Ni（Ⅱ） were prepared and characterized by analytical, spectroscopic （IR, UV-Vis, Mass） techniques, electrical conductivity, magnetic and thermal measurements. The crystal and molecular structure of [Cu（HL）2Cl2] was determined by a single-crystal X-ray diffraction study. The molecular structure of the title compound has an inversion center on the Cu atom.

Syntheses and Crystal Structures of Two Copper(II) Complexes Derived from Bidentate Schiff Bases

Two new Cu（Ⅱ） complexes have been synthesized with two different bidentate N2O2 donor Schiffbase ligands HL1 （2-（（E）-（4-chlorophenylimino）methyl）-6-bromo-4-chlorophenol） and HL2 （2-（（E）-（2-chlorophenylimino）methyl）-6-bromo-4-chlorophenol）, respectively. Both complexes 1 and 2 have been characterized by elemental analysis and single-crystal X-ray diffraction studies. Structural studies reveal that in both complexes the metal centers are four-coordinated with N202 donor set of Schiff base ligands. Complex 1 belongs to the tetragonal system, space group P4（3）2（1）2 with a = 10.2379（2）, b = 10.2379（2）, c = 24.9623（90） A, V = 2616.41（12） A^3, Z = 4, Dc = 1.908 g/cm^3,μ（MoKa） = 4.3327 mm^-1, F（000） = 1468, S = 0.999, the final R = 0.0345 and wR = 0.0835 for 3506 unique reflections （Rint= 0.0428） with 3249 observed ones （I 〉 2σ（I））. Complex 2 is of monoclinic system, space group P21/c with a = 11.064（3）, b = 9.437（2）, c = 13.277（4） A, fl = 108.997（3）°, V = 1310.8（6） A^3, Z = 2, Dc= 1.904 g/cm^3,μ（MoKa） = 4.319 mm^-1, F（000） = 734, S = 0.997, the final R = 0.0282 and wR = 0.0619 for 3491 unique reflections （Rint = 0.0428） with 2777 observed ones （I 〉 20（I））. The units of the complex are linked via weak interactions, such as C-H…Br hydrogen bonds together with Cl…C1 and Cu…Cl interactions, leading to the formation of one-dimensional chain and two-dimensional network and stabilizing the crystal structure.

Synthesis and Crystal Structure of a Novel Binuclear Cu(Ⅱ) Complex with Tetradentate Schiff-base Ligand

A novel binuclear complex （[Cu^2（μ2-shed）（hshed）].（CIO4）,H2O, h2shed = N-salicylidene-N＇-（2-hydroxyethyl）ethylenediamine） has been synthesized and structurally characterized by X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 12.511（10）, b = 15.750（12）, c = 14.281 （12） A, β = 100.564（14）°, C22H31CIN4O9Cu2, Mr = 658.04, V = 2766（4） A^3, Z = 4, Dc = 1.580 g/cm^3,μ（MoKα = 1.689 mm^-1, F（000） = 1352, the final R = 0.0528 and wR = 0.1433 for 4880 independent reflections with Rint = 0.0577. The complex is a binuclear copper compound, and two Cu（Ⅱ） ions in the binuclear cation are in different coordination environments. The Cu（1） ion adopts a distorted square pyramidal geometry （x = 0.22） with four donor atoms （N2O2） of the ligand in the basal plane, and one hydroxyl oxygen atom with protonated form occupying the apical position. The Cu（2） ion assumes the geometry of a distorted square plane with four donor atoms （N2O2） of the ligand. The Cu...Cu separation is 3.103 A,. In addition, N-H…O and C-H…O intermolecular hydrogen bonding interactions link these binuclear cations into a quasi one-dimensional chain along the a axis.

Synthesis and Crystal Structure of a Bimetallic Cyanide-bridged Complex Derived from Manganese(Ⅲ) Schiff-base Complex and Pentacyanidonitrosylferrate(Ⅱ) Building Blocks

A new cyanide-bridged bimetallic assembly [Mn（3-meosalpn）（H2O）]2[Fe（CN）5NO]（1） was obtained by the reaction of [Fe（CN）5NO]2-with [Mn（3-meosalpn）]＋,and characterized by elemental analysis,IR and single-crystal X-ray structure analysis.The complex crystallizes in the monoclinic system,space group P21/c with a = 12.992（5）,b = 13.274（6）,c = 14.644（6） ,β = 115.198（4）o,V = 2285.2（16）3,Z = 2,C43H44FeMn2N10O11,Mr = 1042.61,Dc = 1.515 g/cm3,F（000） = 1072,μ = 0.928 mm-1,S = 1.052,the final R = 0.0347 and wR = 0.0957 for 17377 observed reflections（Ⅰ 〉 2σ（Ⅰ））.X-ray single-crystal diffraction analysis reveals that 1 has a trinuclear molecular structure,in which the two [Mn（3-meosalpn）（H2O）]＋ cations are linked by the central [Fe（CN）5NO]2-anion via two trans CN-groups.Furthermore,the two [Mn（3-meo-salpn）（H2O）]＋ cations and [Fe（CN）5NO]2-anion are connected into a one-dimensional zigzag chain through hydrogen bonding interactions.

Synthesis and Crystal Structure of Zn(II) Complex with Tridentate Ligand N-(2-Hydroxy-1-naphthylidene)-L-serine

A new Zn（Ⅱ） complex, [Zn（L）2（H2O）2], where H2L = N-（2-hydroxy-1-naphthyli- dene）-L-sedne, has been synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to monoclinic system, space group C2/c with a = 13.669（2）, b = 6.4657（9）, c = 31.463（5） A, β = 98.010（2）°, V = 2753.6（7） A^3, Z = 8, Mr = 358.64, Dc = 1.730 g/cm^3, F（000） = 1472,μ（MoKa） = 1.814 mm^-1, the final R = 0.0355 and wR = 0.0706. The Zn（Ⅱ） atom adopts a square-pyramidal geometry coordinated by the tridentate ligand and two water molecules. Intermolecular hydrogen bonds link the complex molecules into a two-dimensional layer.

Synthesis and Crystal Structure ofa Bipy Bridged Binuclear Cu^Ⅱ Complex Containing Aminomethanesulfonic Acid [Cu2（Sams）2（Bipy）（H2O）2]·（H2O）

The title complex [Cu2（Sams）2（H2O）2（bipy）]·（H2O） 1 （H2Sams = N-（2-hydroxybenzy） aminomethanesulfonic acid, bipy = 4,4′-bipyridine） has been synthesized by the reaction of Cu- （CH3COO）2·H2O, nESams and 4,4′-bipyridine in aqueous methanol. It was characterized by IR, elemental analysis, thermogravimetric analysis （TGA） and X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group P21/n with a= 10.9533（17）, b = 8.3408（13）, c = 16.714（3） A^°, β = 101.295（4）°, V = 1494.3（4） A^°3 and Z = 2. The asymmetric unit is comprised of a tridentate Schiff base Sams^2- anionic ligand, a 4,4′-bipyddine and two coordinated water molecules, thus forming a binuclear copper（Ⅱ） complex. The coordination environment at Cu^Ⅱ center is described as a slightly distorted square pyramidal geometry. Via intermolecular hydrogen bonds C（10）-H（10）…O（3） and C（13）- H（13）…O（3）, an infinite supramolecular chain is yielded. A number of intermolecular hydrogen bonds greatly contribute to the stabilization of the solid-state structure for 1.

Synthesis and Crystal Structure of a Copper(II) Complex with 2,4-Dihydroxybenzylidene Benzoylhydrazone Ligand

A new copper（Ⅱ） complex with formula CuL（py）, where L^2- is the dianion of 2,4-dihydroxybenzylidene benzoylhydrazone, has been synthesized and characterized by IR spectra and single-crystal X-ray diffraction method. The crystal belongs to monoclinic, space group P2 1/c with a=0.9630（4）, b=1.4808（6）, c=1.2320（5） nm, β=104.969（6）°, V=1.6973（Ⅱ） nm^3, Z=4, Dc=1.553 g/cm^3,μ（MoKa）=1.311 mm^-1, F（000）=812, R=0.0694 and wR=0.1727 for 1511 observed reflections （I〉2σ（I））. The crystal structure analysis indicates that the copper（Ⅱ） ion lies in a distorted square-planar environment composed of two oxygen atoms, one nitrogen atom from the tridentate acylhydrazone Schiff base ligand L^2- and one nitrogen atom from the pyridine ligand. Two adjacent molecules are connected via weak Cu…O bonding interactions to form dimers, which are further linked to generate a two-dimensional layer structure via interdimeric hydrogen bonds.

Crystal Structure and Characterization of 2-N-(2-Hydroxy-benzylidene) Furanmethanoamine Nickel(II) Complex

The Ni（Ⅱ） complex with ligand 2-N-（2-hydroxy-benzylidene） furanmethanoamine has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c with a = 2.0280（4）, b =0.57700（12）, c = 1.7340（4） nm, β = 94.74（3）°, Z = 4, Dc = 1.508 g/cm^3, the final R = 0.0434 and wR = 0.1112 for 1843 observed reflections with 1 〉 2σ（I）. X-ray analysis revealed that the Ni（Ⅱ） ion is coordinated by two nitrogen atoms of Schiff base and two oxygen atoms of salicylaldehyde in the equatorial plane, and the coordination geometry can be described as a square.

Synthesis, Crystal Structure and Electrochemistry Properties of a (N,N'-Ethylene-bis(salicylaldiminato)) Nickel(II) Complex, [Ni_2(salen)_2]·NCS·NH_4

A new Ni（Ⅱ） complex [Ni2（salen）2]·（NCS）·NH4 （salen = N,N＇-bis（salicylideneamino）ethanato） has been prepared and structurally characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. It crystallizes in the orthorhombic system, space group Pbca with a = 16.8725（13）, b = 19.0046（15）, c = 20.0583（16）A, Z = 8, V = 6431.8（9）A^3, C33H32N6Ni2O4S1, Mr = 726.13, Dc = 1.500 g/cm^3, F（000） = 3008, μ = 1.284 mm^-1, the final R = 0.0394 and wR = 0.0767 for 4449 observed reflections with I 〉 2σ（I）. The complex involves a N,N＇-ethylene-bis（salicylaldiminato） Schiff base, an isothiocyanato anion and an ammonium cation. The nickle（II） ion adopts a distorted square coordination geometry with N2O2 set of Schiff base ligand. The complexes are linked into a dimmer via intermolecular hydrogen bonds and the [Ni（salen）] moieties are connected together to form a 2-D layer structure by intermolecular N-H…O hydrogen bonds and π-π stacking. Cyclic-voltammetry method was used to characterize electrochemically the complex.

Syntheses,Crystal Structures and Thermal Properties of Two Dicadmiun(II) Complexes Cd_2L_2X_2(HL=N-(3-Methoxylsalicylidene)-3-dimethylaminopropylamine,X = Cl(1),NCS(2))

Two Cd（Ⅱ） complexes, Cd2L2Cl2 （1） and Cd2L2（NCS）2 （2） （HL = N-（3-methoxylsalicylidene）-3-dimethylaminopropylamine） were synthesized and determined by EA, IR, TG and single-crystal X-ray diffraction. The crystallographic data are as follows： monoclinic, space group P21/n, a = 9.2710（9）, b = 18.0069（18）, c = 18.5562（19） A^°, β= 99.741（4）°, V = 3053.1（5）, Z = 4,μ = 1.605, F（000） = 1536, R = 0.0264 and wR = 0.0699 for 1; orthorhombic, space group Pca21, a = 16.196（3）, b = 11.506（2）, c = 36.126（7） A^°, V = 6732（2）, Z = 8,μ = 1.428, F（000） = 3264, R = 0.0376 and wR = 0.0877 for 2. There are two geometrically different octahedral Cd（Ⅱ） atoms, with N4O2 and O4Cl2 donor sets for 1 while N4O2 and N2O4 for 2. In the dinuclear Cd（Ⅱ） centers, the Cd（Ⅱ） atoms are held together by two deprotonted phenolate oxygen atoms from tetradentate L^- ligands. The thermal gravity data show two step decompositions with the residues of CdO for two complexes.

Synthesis and Crystal Structure of Bis(S-methyl-β-N- (4-dimethylaminophenyl)methlenedithiocarbazate) Nickel (Ⅱ)

Reaction of nickel (Ⅱ) acetate with S-methyl-β-N-(4 dimethy-laminophenyl) methlenedithiocarbazate gave a mononuclear complex [Ni (C11H14N3S2)2]. Crystal of the title compound belongs to monoclinic systern,space group C2/cwith cell parameters a= 18. 785 (1), b= 17. 274 (1 ), c= 8. 344 (1 ) A, β= 108. 64(2)°, V= 2565(1 ) A3, Z=4, Mr= 563. 36, Dc= 1. 459 g/cm3; μ=10. 05 cm-1 andF(000) = 1176. The final refinement with 2179 observed reflections is converged withR= 0. 044 and R.= 0. 069. X-ray crystal structure analysis revealed that the coordina-tion geometry of Ni (Ⅱ) is a square-planar with two equivalent Ni -N and Ni - Sbonds. The Schiff-base ligand loses a proton from its tautomeric thiol form and is coor-dinated to the nickel atom via the mercapto sulphur and the β-nitiogen.

Synthesis，Crystal Structure of N－Salicylidene－o－aminobenzoic Acid Dipyridine Copper（Ⅱ） Monohydrate

The blue crystal of the title complex N-salicylidene-o-aminobenzoic acid dipyridine Cu（Ⅱ） monohydrate,C24H19CuN3O3·H2O, was obtained and examined by the X-ray single crystal diffraction determination. Crystal data are:Mr=478.99.monoclinic system.space group Cc,Z=4;a=8.431（2）,b=16.568（3）,c=15.885（5）,β=102.97（3）°; V=2162 3,Dc=1.47 g/cm￣3,μ=10.46 cm￣（-1）,F（000）=988.The final agreement factors are R=0.045 and Rω=0.052 for 1327 unique reflections[I≥3σ（I）]. The complex is five-coordinated.in which the Cu（Ⅱ） ion has a pseudo-square geometry,with one N atom and two O atoms as coordinated atoms.

新型不对称双Schiff碱Cu(Ⅱ),Zn(Ⅱ)异三核配合物的合成和晶体结构

合成了不对称双Schiff碱Cu(Ⅱ)单核配合物CuHL(H3L为N3羧基水杨醛N′水杨醛缩乙二胺)及其Cu(Ⅱ)Zn(Ⅱ)Cu(Ⅱ)异三核配合物。用元素分析、红外光谱、电子光谱对它们进行了表征,用X射线单晶衍射法测定了三核配合物的晶体结构。该三核配合物属三斜晶系,P1空间群,晶胞参数为a=11862(2)nm,b=15440(3)nm,c=19488(4)nm;α=9004(3)°,β=9786(3)°,γ=9012(3)°;V=35356(12)nm3,Z=1;R1=00614,wR2=01319。

N,N,N-三齿席夫碱铜(Ⅱ)配合物的合成、晶体结构及儿茶酚酶活性

选用N,N,N-三齿席夫碱化合物2-氨基乙基苯并咪唑缩吡啶-2-甲醛(L^(1))和2-氨基丙基苯并咪唑缩吡啶-2-甲醛(L^(2))为配体,与过渡金属Cu(Ⅱ)盐反应合成了4个单核铜配合物:[Cu(L^(1))Cl_(2)](1),[Cu(L^(1))(SCN)_(2)](2),[Cu(L^(1))bpy](ClO_(4))_(2)·CH_(3)OH(3)和[Cu(L^(2))bpy](ClO_(4))_(2)(4)(bpy=2,2′-联吡啶).通过元素分析、红外光谱、粉末X射线衍射、单晶X射线衍射、热重分析和循环伏安分析等手段对配合物进行了表征.结果表明,在固体状态下,配合物1~4均为单核Cu(Ⅱ)配合物,中心Cu(Ⅱ)均为畸变四方锥构型,结构参数τ=0.088~0.340.以3,5-二叔丁基邻苯二酚为底物,研究了配合物1~4模拟儿茶酚氧化酶的催化活性,采用Michaelis-Menten模型和Lineweaver-Burk图法计算了动力学参数.结果表明,配合物均具有儿茶酚氧化酶活性,催化活性顺序为2>3≈4>1,氧化速率取决于Cu(Ⅱ)配位环境的畸变程度、离去基团与中心Cu(Ⅱ)的键长和配合物的空间位阻.