Syntheses and Anti-lung Cancer Effects of Two Novel Dy(Ⅲ) Complexes Based on 1,3,5-Benzenetricarbocylic Acid and 1,3,5-Benzenetrisbenzoic Acid,respectively

The reactions of 1,3,5-benzenetricarbocylic acid(H3BTC) and 1,3,5-benzenetrisbenzoic acid(H3BTB) with Dy(NO3)3·6H2O afford two novel Dy(III) coordination polymers respectively, Dy(BTC)(H_2O)DMF(1) and [Dy(BTB)(Et OH)](DMF)(2)(DMF = N,N-dimethylformamide). 1 shows a 3D framework composed of available Lewis-acid metal sites which are occupied by the coordinated water molecules, and 2 features a noninterpenetrated open 3D framework with a 5-connected bnn hexagonal topology possessing the point symbol(46.64). In addition, in vitro antitumor activities of compounds 1 and 2 on three human lung cancer cells(H1975, HCC827 and A549) were further determined.     

Syntheses,Crystal Structures and DNA-Binding Properties of Zn(Ⅱ)and Mn(Ⅱ)Complexes Based on Imidazole Derivatives and Carboxylic Acid

Complexes[Zn(pbm)(5-hip)3](1),[Zn(pbm)(5-nip)3](2),[Mn(pbm)(H3btc)2(H2O)](3)and[Mn(pbm)(5-nip)3](4),where H2HIPA=5-hydroxyisophthalic acid,H2nip=5-nitroisophtha...     

Syntheses,Crystal Structures and Antibacterial Activities of Schiff Base of Nickel(Ⅱ) and Copper(Ⅱ) Complexes

A new kind of Schiff base HL(HL= 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-Leucine methyl ester) and complexes Ni L′_2·0.75C_2H_5OH·0.25H_2O,Cu L′′2(L′ = 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-leucine ethyl,L′′ = 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-leucine) have been synthesized and structurally determined by X-ray diffraction. For HL: crystal structure determination indicates that there are two independent HLs with different conformations in one asymmetric unit. For complex 1: the Ni(Ⅱ) ion is six-coordinated by two carbonyl oxygen atoms from pyrazolone ring,two nitrogen atoms from different HL′ and two oxygen atoms from L-Leucine ethyl ester to form a distorted octahedral geometry. For complex 2: the Cu(Ⅱ) ion is four-coordinated by one carbonyl oxygen atom from the pyrazolone ring,one nitrogen atom from HL′′,and two different carboxylic oxygen atoms from L-leucine with the same conformation to form a distorted quadrilateral geometry.     

Syntheses,Crystal Structures and Properties of Mn(Ⅱ) and Co(Ⅱ) Coordination Complexes Based on 1,10-Phenanthroline Derivative

Two new coordination complexes[Mn(L)₂(DNSA)](1) and[Co(L)(1,4-bdc)]_n (2) have been achieved under hydrothermal conditions (H₂DNSA=3,5-dinitro-salicylic acid,1,4-bdc=1,4-benzenedicarboxylic acid and L=2-(2-fluoro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline).1 crystallizes in monoclinic,space group P2_1/c with a=15.871(3),b=17.274(4),c=16.078(3)A,β=113.03(3)^o,V=4056.6(16)A³,Z=4,C₄₅H₂₂Cl₂F₂Mn N₁₀O₇,M_r=978.57,D_c=1.602 g/cm³,F(000)=1980,μ(Mo Ka)=0.536 mm^–1,R=0.0437 and w R=0.1065.2 belongs to the monoclinic system,space group C2/c with a=14.665(2),b=30.856(4),c=11.237(2)A,β=111.166(2)^o,V=4742.0(12)A³,Z=8,C₂₇H₁₄Cl Co FN₄O₄,M_r=517.80,D_c=1.602 g/cm³,F(000)=2312,μ(Mo Ka)=0.889 mm^–1,R=0.0364 and w R=0.0862.The central Mn(II) ion in 1 is six-coordinated by four nitrogen atoms from two L ligands and two oxygen atoms from one DNSA anion.In 2,the two kinds of 1,4-bdc ligands link neighboring Co(II) atoms to yield a two-dimensional layer structure.The luminescence of 1 has been studied in detail.Moreover,thermal behaviors of 1 and 2 are also investigated.     

Syntheses,Crystal Structures and Magnetic Studies of Two Mn(Ⅱ) Complexes Based on 2-Pyrimidineamidoxime

Two novel manganese(Ⅱ) complexes, [Mn(pmadH_2)_2(3-Sb)]n(1) and {[Mn(pmadH2)(Hssal)(H_2O)]·2 H_2O}n(2)(pmadH_2= 2-pyrimidineamidoxime, 3-Sb = 3-sulfobenzoate dianion, H_3ssal = 5-sulfosalicylic acid), have been successfully obtained. The two complexes were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermal gravimetric analysis, infrared spectra and elemental analysis. They are one-dimensional manganese polymer(1) and two-dimensional manganese complex(2), respectively. The values of χmT at 300 K of 1 and 2 are lower than the spin-only value for the non-interacting Mn(Ⅱ) ion(S = 5/2).     

Syntheses,Crystal Structures and DNA-binding Properties of Cd(Ⅱ), Co(Ⅱ), Cu(Ⅱ) and Zn(Ⅱ) Complexes Containing Imidazolium Derivatives

Cd(Ⅱ), Co(Ⅱ), Cu(Ⅱ) and Zn(Ⅱ) complexes(1~4) based on 2-(2-pyridyl)benzimidazole(pbm) and 4,4'-oxybisbenzoic acid(H2odc) were synthesized. The formulas of these complexes are [Cd(pbm)(odc)2](1), [Co(pbm)(odc)2](2), [Cu(pbm)(odc)2](3) and [Zn(pbm)(odc)2](4) confirmed by single-crystal X-ray diffraction analysis, which shows that complexes 1, 2 and 4 belong to monoclinic system with space group P21/n, while complex 3 belongs to monoclinic system with space group P21/c. The binding properties of complexes 1~4 with CT-DNA are evaluated by ultraviolet spectrum, fluorescence spectra and viscosity measurements. The results indicate that complexes 1~4 have strong interaction with CT-DNA binding. These complexes exhibit an electrostatic or groove mode in respect of binding with DNA, which can effectively destroy DNA. And this binding mode may be applied to the interaction between the complexes and cancer cell DNA. Therefore, we hope to provide a theoretical and scientific basis for the research of anti-cancer drugs.     

Hydrothermal Syntheses,Crystal Structures and Luminescence Properties of Zn(Ⅱ) and Cu(Ⅱ) Complexes Based on 2,2'-((Sulfonylbis(4,1-phenylene))bis(oxy))diacetic Acid

The 2,2'-((sulfonylbis(4,1-phenylene))bis(oxy))diacetic acid(H2L) and 4,4'-bipyridine(4,4'-bipy) are employed as organic ligands to react with metal salts to obtain two new metal-organic frameworks(MOFs), namely [M2L2(4,4'-bipy)](M = Zn(1), Cu(2)). They have been successfully synthesized under hydrothermal conditions. Single-crystal X-ray diffraction reveals that two complexes are isostructural and crystallize in orthorhombic system with space group Pbcn. All L^2- ligands bridge metal ions to form an infinite 1D Z-shaped chain along the a axis. Then through 4,4'-bipy, contiguous Z-shaped chains are linked to form a 2D layer structure. The luminescent studies of the H2L ligand and complex 1 in the solid state and thermogravimetric analyses(TGA) of two complexes are investigated.     

Syntheses,Crystal Structures and Luminescent Properties of Two New Zinc(Ⅱ) Complexes Based on Bifunctional Ligand

By using solvothermal method,two novel coordination polymers based on 4-(4-carboxyphen-yl)-1,2,4-triazole(Hcpt) and Zn(Ⅱ) cations,[Zn(cpt)(OH)]_n·n H_2O(FJU-32) and [Zn(cpt)(atrz)]n(FJU-33)(Hatrz = 3-amino-1,2,4-triazolate),were synthesized and characterized by single-crystal X-ray diffraction analyses,elemental analyses,FT-IR and powder X-ray diffraction. FJU-32 crystallizes in monoclinic,space group P21/c with a = 3.7441(3),b = 23.0384(19),c = 11.8562(10) ?,β = 99.069(8)o,V = 1009.91(15) ?3,Dc = 1.898 g/cm3,C_9H_9N_3O_4Zn,Mr = 288.57,F(000) = 916,μ(MoKα) = 2.439 mm~(-1),Z = 4,R = 0.0600 and wR = 0.1306 for 2412 observed reflections(I 2σ(I)),and R = 0.0704 and wR = 0.1349 for all data. FJU-33 crystallizes in monoclinic space group P21/c with a = 12.7483(5),b = 9.9922(3),c = 9.8403(3) ?,β = 100.756(4)°,V = 1231.47(7) ?~3,Dc = 1.816 g/cm~3,C_(11)H_9N_7O_2Zn,Mr = 336.62,F(000) = 680,μ(Cu Kα) = 2.957 mm~(-1),Z = 4,R = 0.0478 and w R = 0.1184 for 2466 observed reflections(I 2σ(I)),and R = 0.0687 and w R = 0.1309 for all data. In FJU-32,Zn(Ⅱ) is coordinated to three μ3-OH groups forming an unprecedented 1D zigzag-like double chain,and the 1D double chains are connected to four neighbouring double chains by the cpt ligands to form an extended 3D porous coordination polymer. In FJU-33,the adjacent [Zn(atrz)] 2D layers are further connected by the cpt ligands via Zn–O coordinated bonds and neighboring interlayer hydrogen-bonding interactions to give rise to an overall 3D pillared layer structure. The neutron triazole group of the cpt ligand has weaker coordination ability than the triazolate anion of atrz ligand. Furthermore,FJU-32 and FJU-33 display high thermal stability up to 300 ℃,and the solid state fluorescence reveals that two new complexes are potential optical materials.     

Syntheses,Structures and Anticancer Activities of Three 4(3H)-Quinazolinone Cd(Ⅱ) Complexes

The title complexes based on 4(3H)-quinazolinone ligand have been synthesized and characterized by elemental analysis, IR spectrum and single-crystal X-ray diffraction analysis.Complex 1 belongs to the triclinic system, space group P1, with a = 6.5392(3), b = 7.4402(5), c =10.3397(7) ?, α = 83.204(5), β = 75.465(5), γ = 86.075(5)° and V = 483.88(5) ?~3. Complex 2 is of orthorhombic system, space group Pbca, with a = 10.1294(3), b = 7.6747(5), c = 23.8171(15) ? and V = 1849.1(4) ?~3. Complex 3 belongs to the orthorhombic system, space group Pbca, with a =12.7188(2), b = 6.66582(9), c = 25.6987(6) ? and V = 2178.77(5) ?~3. The complex structures are affected by the synthesis conditions.     

Syntheses,Crystal Structures and Anticancer Activities of Dithiocarbamate Bismuth(Ⅲ) Complexes

Two novel complexes, [Bi(III)(S2CNBn Et)3] 1 and [Bi(III)(S2CNPPPy-2)3] 2, were synthesized and characterized by elemental analysis, IR, 1H NMR, 13 C NMR, TG-DTG and X-ray single-crystal diffraction. The structure reveals that complex 1 belongs to the monoclinic system, space group P21/c with a = 11.457(5), b = 17.437(8), c = 33.439(14), β= 98.499(8)o, Z = 4, V = 6607(5)3, Dc = 1.689 g·cm-3, F(000) = 3328, μ= 5.742 mm-1, the final R = 0.0906, w R = 0.1678 and S = 1.032. The structure indicates that complex 2 belongs to the triclinic system, space group P1 with a = 12.608(9), b = 12.622(8), c = 12.49(6), α = 102.652(15), β = 103.013(14), γ = 109.698(10)o, Z = 1, V = 1762.3(19)3, Dc = 1.741 g·cm-3, F(000) = 916, μ = 5.395 mm-1, the final R = 0.048 2, w R = 0.1206 and S =1.046. In the two complexes, each six-coordinated Bi(III) atom adopts a pentagonal pyramidal configuration with six sulfur atoms from three ligands, and the dimmer structures are formed by weak interactions of Bi···S between two molecules. The anticancer activities of the two complexes were studied by evaluating their cytotoxicities against several human cancer cell lines using the MTT assay. Results indicated complex 2 showed moderate cytotoxic effects on the selected cancer cells.     

Syntheses,Structures and Photoluminescent Properties of Cd(Ⅱ) Polymeric Complexes Based on 5-Aminoisophthalic Acid and Bipyridine Co-ligands

Two novel complexes, namely {[Cd(AIP)(4,4?-bpy)]·1.3DMF}n(1) and [Cd(AIP)(2,2?- bpy)]n(2), have been synthesized through solvothermal reaction(H2AIP = 5-aminoisophthalic acid, 2,2?-bpy = 2,2?-bipyridine, 4,4?-bpy = 4,4?-bipyridine, and DMF = N,N?-dimethylformamide) and structurally determined by single-crystal X-ray diffraction. Complex 1 shows a three-dimensional(3D) layer-pillar framework with rectangular channels, while complex 2 displays a two-dimensional(2D) wave net architecture. Furthermore, 1 and 2 were characterized by elemental analysis, infrared spectra(IR), thermal gravimetric analyses(TGA) and fluorescence measurements. The luminescent properties of 1 dispersed in various organic solvents have been investigated systematically, demonstrating high selectivity for acetone via the fluorescence quenching effect.     

Syntheses and Crystal Structures of Three Coordination Complexes Based on Ln(Ⅲ) and mpca-Ligand

Three complexes obtained by the reaction of Pr(Ⅲ) or Nd(Ⅲ) salts with 5-methyl-2-pyrazinecarboxylic acid(Hmpca) are structurally determined by single-crystal X-ray diffraction.Complex [Pr(mpca-)3(H2O)2]2·6H2O(1) is composed of dinuclear Pr(Ⅲ) units with two metal centers bridged by two anionic mpca-ligands in a κ3O,O':O' bridging mode.Complexes [Pr(mpca-)3]n(2) and [Nd(mpca-)3]n(3) are isostructures,and they consist of polymeric chains based on Ln(Ⅲ) and mpca-ligands.Each pair of adjacent metal centers is linked by three mpca-molecules in a κ3N,O:O bridging mode.     

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) ?, 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) ?, β = 111.237(14)°, V = 3017(4) ?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.     

Syntheses and Characterizations of Cd(Ⅱ) and Pr(Ⅲ) Complexes Based on 5-(Tetrazol-5-yl) Isophthalic Acid

Hydrothermal reactions of 5-(tetrazol-5-yl) isophthalic acid with cadmium nitrate/praseodymium nitrate led to two complexes of [Cd_3(TZI)_2(H2_O)_(11)]_n(1) and [Pr(TZI)(H_2O)_5]_n(2). Their structures and properties were determined by X-ray diffraction, IR spectroscopy, fluorescence spectrum, thermal gravimetric analyses and elemental analysis. Complex 1 belongs to monoclinic system, I2/c space group, with a = 12.8688(3), b = 18.0925(3), c = 14.5190(3) ?, β = 116.054(3)°, V =3036.92(13) ?~3, Z = 4; complex 2 crystallizes in triclinic, space group P 1, with a = 7.9690(5), b =9.7665(8), c = 10.4353(9) ?, α = 116.709(9), β = 107.461(6), γ = 95.671(6)°, V = 665.54(9) ?3 and Z =2. Complex 1 is a 3D planar structure. Complex 2 is a one-dimensional double chain configuration and extends into a 3D network by hydrogen bonds and π-π interactions.     

Two Cd(Ⅱ) and Cu(Ⅱ) Complexes Based on 1-Butylbenzimidazole: Crystal Structures and Weak Interactions

1-Butylbenzimidazole L reacted with Cd(NO3)2·4H2O to afford complex [CdL(NO3)3H2O]·[HL] 1. The heptacoordinated Cd(Ⅱ) center adopts a distorted pentagongal bipyramidal geometry, and complex [CdL(NO3)3H2O]-entity and the protonated benzimidazium salt [HL]+ are connected via N-H···O hydrogen bond to form a dimeric unit [CdL(NO3)3H2O]·[HL]. A 3-D supramolecular network of 1 is formed through N-H···O and O-H···O hydrogen bonds together with π-π stacking interactions. Reaction of L with CuCl2 afforded a mononuclear complex, [CuL2Cl2] 2, in which the tetracoordinated Cu(II) center adopts a distorted tetrahedral geometry. In contrast, 2-D supramolecular layers of 2 are formed by C-H···Cl hydrogen bonds. The fluorescent emission spectra of L, 1 and 2 are described.     

Syntheses,Characterization and Crystal Structures of Dithiocarbamate-based Mononuclear Palladium(Ⅱ) Complexes

By employing the dithiocarbamate salt(K(PPDC), where PPDC = 4?-pyridyl-1-piperazine-4-dithiocarbamate) as the functional ligand and di-palladium complexes [(N^N)_2Pd_2(NO_3ˉ)_2](NO3ˉ)2(N^N = 2,2?-bipyridine, bpy; 4,4?-dimethylbipyridine, dmbpy) as corner, two novel single metal complexes with Pd(II) centers have been obtained. These organic-metal complexes were characterized by NMR, ESI-MS, elemental analysis, Uv-vis spectra and single-crystal X-ray diffraction analysis. Compound 1·(PF6)2([(bpy)Pd(PPDC)]·(PF6)2) crystallizes in triclinic, space group P1, a = 8.3968(5), b = 11.5565(7), c = 18.2234(11) ?, α = 97.505(1), β = 91.424(1), γ = 106.146(1)o, C22H24N6S2P2F12 Pd, Mr = 832.93, V = 1680.58(18) ?~3, Z = 2, Dc = 1.646 Mg/m3, μ(MoK α) = 0.863 mm-1, F(000) = 828, the final R = 0.0455 and wR = 0.1390 for 6981 observed reflections with I 2σ(I). Similarly, compound 2·(PF6)2([(dmbpy)Pd(PPDC)]·(PF6)2) also crystallizes in triclinic, space group P1, a = 13.9467(3), b = 14.8390(2), c = 17.0632(3) ?, α = 81.8680(10), β = 87.051(2), γ = 83.4590(10)o, C_(22)H_(25)N_5S_2P_2F_(12)Pd, M_r = 819.93, V = 3470.81(11) ?~3, Z = 4, D_c = 1.569 Mg/m~3, μ(CuK α) = 7.115 mm~(-1), F(000) = 1632, the final R = 0.0606 and w R = 0.1637 for 12835 observed reflections with I 2σ(I). Crystallography reveals that each metal center coordinates with two N atoms from bpy and two S atoms from PPDC in the square coordination mode. In the crystal structure of complex 1, a weak Pd···Pd interaction can be observed. Interestingly, it was also found that the mononuclear moieties of complex 2 could be packed into a 3-D porous framework via multiple intermolecular C–F···H hydrogen-boding interactions which extended in the a, b, and c axes with PF_6ˉ anions frozen inside.     

Crystal Structures and Characterizations of Bis(pyrrolidinedithiocarbamato)Cu（Ⅱ） and Zn(Ⅱ） Complexes

The structures of [Cu (S₂CN (CH₂)₄)₂] (1) and [Zn₂(S₂CN‐(CH₂)₄)₄] (2) have been determined by X‐ray crystallography analysis. They are all isomorphous and triclinic, space group of P1^?, with Z = 1. The lattice parameters of compound 1 is: a = 0.63483(2) nm, b = 0.74972(3) nm, c=0.78390(1) mn, α = 75.912(2)°, β = 78.634(2)° and γ = 86.845(2)°; compound 2: a = 0.78707(6) nm, b=0.79823(6) nm, c = 1.23246(9) nm, α = 74.813(2)°, β = 73.048(2)° and γ = 88.036(2)°. The copper atom is located on a crystallographic inversion center and zinc atom lies across centers of symmetry. The Cu(II) ion has a square‐planar geometry while Zn(II) has a distorted tetrahedral geometry. The thermal gravity (TG) data indicate that no structural transitions in the two compounds were abserved and the decomposition products can adsorb gas. Also they all have a high thermal stability.