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...     

Synthesis and Crystal Structure of a New Complex Zn(Ⅱ)L_2·2CH_3OH(H_2L = 4-Chloro-2-(2,3-dihydro-1H-benzoimidazol-2-yl)-phenol)

A new complex Zn(Ⅱ)L2·2CH3OH(H2L = 4-chloro-2-(2,3-dihydro-1H-ben-zoimi-dazol-2-yl)-phenol) has been prepared and characterized by single-crystal X-ray diffraction analysis and elemental analysis.The crystal is of triclinic system,space group P1 with a = 9.2905(10),b = 10.3555(13),c = 14.9590(14) ,α = 101.0340(10),β = 101.261(2),γ = 99.1660(10)o,V = 1356.1(3) 3,Z = 2,C28H24Cl2N4O4Zn,Mr = 616.78,Dc = 1.510 g/cm3,μ = 1.145 mm·1,F(000) = 632,the final R = 0.0379 and wR = 0.0830 for 3606 observed reflections with I 2σ(I).The Zn(Ⅱ) atom presents a distorted square pyramidal coordination involving two H2L ligands.The hydrogen bonds and π···π stacking interactions extend the complex into a two-dimensional framework.     

Syntheses,Structures and Characterizations of Two New Zinc(Ⅱ) Coordination Polymers Constructed from 3-(1H-Pyrazol-4-yl)-5-(pyridin-2-yl)-1,2,4-triazole and Different Carboxylate Ligands

Two new zinc(Ⅱ) coordination polymers, [Zn(ph)(H2 L)·H_2O]2 n(1) and [Zn(ip)(H2 L)-(H_2O)]n(2)(H2 ph = phthalic acid, H2 ip = isophthalic acid, H2L = 3-(1 H-pyrazol-4-yl)-5-(pyridin-2-yl)-1,2,4-triazole), have been successfully synthesized via hydrothermal reaction. It has been structurally characterized by X-ray single-crystal analysis, IR spectra, fluorescence spectroscopy and thermogravimetry analysis. The single-crystal X-ray diffraction studies reveal that compounds 1 and 2 both exhibit 1D chain structures, and assemble into 2D and 3D supermolecules through hydrogen bonds or π-π interactions. Moreover, the thermal stability and luminescent properties of compounds 1 and 2 were also studied.     

Synthesis and Cytotoxicity of the First Arene Ruthenium Compound Containing Two Thiosemicarbazone Ligands

A Ru-arene compound containing two thiosemicarbazone ligands [(η6-p-cymene)Ru(TSC)2 Cl]Cl(1, TSC = benzophenone 4-methylthiosemicarbazone) has been synthesized and characterized by 1 H NMR, elemental analysis and HR-ESI mass spectrometry analysis. The molecular structure was determined by single-crystal X-ray diffraction analysis. The in vitro anticancer activities of the complex have been evaluated against two human cancer cell lines(SGC-7901, BEL-7404), and the IC50 values are 32.5 and 57 μM, respectively.     

Synthesis,Crystal Structure,Fluorescent Property and DFT Study of a Novel 1D Polymer [Zn(HMICD)(bpy)]_n·2nH_2O

A new one-dimensional(1D) polymer, [Zn(HMIDC)(bpy)]_n·2n H_2O(1, H_3MIDC = 2-methyl-imidazole-4,5-dicarboxylic acid, bpy = 2,2?-bipyridine), has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, UV-vis spectrum and fluorescence measurements. Complex 1 crystallizes in orthorhombic system, space group Pbca with a = 14.404(3), b = 8.6900(17), c = 26.570(5) ?, V = 3325.8(11) ?~3, Dc = 1.700 g/cm~3, M_r = 425.70, Z = 8, F(000) = 1744, μ = 1.522 mm~(-1), the final R = 0.0421 and w R = 0.1018. The Zn(Ⅱ) ion is six-coordinated by O and N atoms from one HMIDC ligand, two O atoms from another HMIDC ligand and two N atoms from the bpy ligand. The HMIDC anion, which acts as a tetradentate ligand, chelates two Zn ions to form a one-dimensional(1D) zigzag chain structure. We analyzed the electronic structure and orbital energies of complex 1 by DFT methods, and the results are consistent with the UV-vis spectrum. And we also discussed the luminescent mechanism of complex 1 in detail.     

一个双核锌(Ⅱ)配合物[Zn2(L)2(Mf)2]的合成、结构、热稳定性及荧光性质

The binuclear Zn(Ⅱ) complex [Zn2(L)2(Mf)2] with 2-hydroxyacetophenone benzoylhydrazone (H2L) and monodentate N-heterocycle, morphine (Mf) has been synthesized and characterized by elemental analysis, IR, UV, molar conductivity, TG and X-ray diffraction structural analysis. Crystal data: monoclinic, space group P21/n with 0=1.263 9(6) nm, b=1.085 2(4) nm, c=1.313 4(5) nm, β=92.16(2)°, V=1.800(l) nm3, Z=2, 0C=1.493 g·cm-3,μ= 1.388 mm-1, F(000)=840, and final R =0.038 4, wR =0.087 9. The two Zn(Ⅱ) centers in the centrosymmetric binuclear complex are bridged by phenolic oxygen atoms with Zn…Zn separation of 0.3150(1) nm. The coordination geometry of each Zn(Ⅱ) atom is trigonal bipyramidal. The fluorescence activities of ligand and the complex were also studied. CCDC: 712643.     

Synthesis, Crystal Structure, Thermal Behavior and Photoluminescent Property of Complex [Zn(L)(SO4)]·0.5H2O

Complex [Zn(L)(SO4)]·0.5H2O (L= 2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline) has been synthesized under hydrothermal conditions. The compound was characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21 /n with a = 9.9916(7), b = 12.3834(9), c = 29.259(2) , β = 97.7720(10)°, V = 3587.0(4)3 , Z = 2, C76H41Cl4F4N16O9S2Zn2 , Mr = 1734.91, Dc = 1.606 g/cm 3 , F(000) = 1754, μ(MoKa) = 0.959 mm -1 , R = 0.0492 and wR = 0.1385. The asymmetric unit of 1 contains one Zn(II) atom, two L ligands, one sulfate anion and half a water molecule. Each Zn(II) atom is five-coordinated by four nitrogen atoms from two different L ligands and one sulfate oxygen atom in a tetragonal pyramidal coordination environment. The N-H···O hydrogen bonds link the discrete structure of 1 into a 2D supramolecular architecture. The photoluminescent property of 1 has also been studied in the solid state at room temperature.     

Synthesis and characterization of a new open-framework zinc phosphite (4,4′-(C5H4N)2(CH2)3)·[Zn3(HPO3)4]

Employing 4,4-trimethylenedipyridine as a template,a new two-dimensional zinc phosphite (4,4-(C5H4N)2(CH2)3)· [Zn3(HPO3)4 ] has been prepared at room temperature and characterized by single-crystal X-ray diffraction,FTIR,elemental analysis,powder X-ray diffraction,and thermogravimetric analysis.The compound crystallizes in the monoclinic space group P2 1 /c,with cell parameters,a=9.3309(19),b=14.798(3),c=33.637(7),β=91.11(3),V=4643.8(16) nm 3 and Z=4.The connectivity of the ZnO4 tetrahedra and HPO 3 pseudo pyramids results in infinite corner-sharing 4-membered ring chains as second building units which are further linked by Zn O P bonds to form a 2-D layer that with interesting 8-membered ring channels along the [100] direction.The diprotonated 4,4-trimethylenedipyridine molecules sit in the middle of the layers along the [100] direction and interact with the framework via hydrogen bonds.     

A Novel Zn(Ⅱ) Complex with 4-Connected umc Topology:Synthesis,Crystal Structure and Luminescent Property

A novel complex, [Zn(L)]2·H2O(1, H2 L = 4-aminophthalic acid), has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group C2/c with a = 12.4267(6), b = 7.7482(3), c = 18.6983(8) ?, β = 110.437(3)o, V = 1687.04(13) ?3, Z = 4, C16H12N2O9Zn2, Mr = 507.06, Dc = 1.996 g/cm3, μ = 2.903 mm-1, S = 0.989, F(000) = 1016, the final R = 0.0304 and w R = 0.0720 for 12618 observed reflections(I 2σ(I)). Single-crystal X-ray structural analysis reveals that compound 1 features a three-dimensional(3D) framework with 4-connected umc topology. Moreover, the thermogravimetric(TG) analysis and photoluminescent property of 1 were also discussed.     

Syntheses,Structures,and Photoluminescent Properties of Two Zn(Ⅱ) Coordination Polymers with Helical Chains Structures

Two novel coordination polymers with helical chains, {[Zn(L)(H2O)]?H2O}n(1) and {[Zn(L)(p-bix)]?3.5H2O}n(2), where H2 L = 5-(4-hydroxypyridinium-1-ylmethyl) isophthalic acid and p-bix = 1,4-bis(imidazol-1-ylmethyl)benzene, have been hydrothermally synthesized, and charac-terized by elemental analysis, powder X-ray diffraction(PXRD), IR, thermal gravimetric analyses(TGA) and also by single-crystal X-ray diffraction. Both complexes 1 and 2 crystallize inmonoclinic, space group P21/c. Compound 1 displays a two-dimensional(2D) structure with two distinct types of helical chains; 2 shows a layered coordination polymer with two types of helical chains and features an interesting 2D→3D interdigitated architecture. Meanwhile, the luminescent properties of 1 and 2 have also been investigated in detail.     

Hydrothermal Synthesis and Structural Characterization of a Novel 3-D Open Framework Zinc Phosphate Microporous Compound(C_5N_2H_(14))·[Zn_3(OH_2)(PO_4)_2(HPO_4)]

One novel organically templated zincophophate(C5N2H14)·[Zn3(OH2)(PO4)2(HPO4)] has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction together with elemental analysis, infrared spectroscopy, thermogravimetric analysis, and powder X-ray diffraction. The title compound crystallizes in the monoclinic space group P21/n, with a = 9.7904(11), b = 14.0287(14), c = 11.8651(13) , β = 104.690(3), V = 1576.4(3) 3, Z = 4, T = 296(2) K, Mr = 601.31 and Dc = 2.533 g/cm3. The compound consists of a macroanionic [Zn3(OH2)(PO4)2(HPO4)]2- framework and(C5N2H14)2+ cations, and its structure is built up from ZnO3(OH2), ZnO4, HPO4 and PO4 tetrahedral units that result in 4, 8 and 10-ring channels.     

Synthesis,Crystal Structure and Luminescent Property of a Zn(Ⅱ) Complex Based on 4-Imidazole-carboxylate Ligand

A new complex, [Zn(L)_2](1), has been hydrothermally prepared by the reaction of ZnSO_4·7H_2O with 2-(1H-imidazol-4-yl)benzoic acid(HL) incorporating 4-imidazolyl and carboxylate functional groups, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and powder X-ray diffraction(PXRD). Complex 1 crystallizes in monoclinic, space group C2/c with a = 9.8349(9), b = 7.4947(7), c = 24.104(2) ?, β = 92.889(2)o, V = 1774.4(3) ?~3, Z = 4, C_(20)H_(14)N_4O_4 Zn, M_r = 439.72, D_c = 1.646 g/cm~3, μ = 1.422 mm~(-1), S = 1.003, F(000) = 896, the final R = 0.0395 and wR = 0.0874 for 11386 observed reflections(I 2σ(I)). Single-crystal X-ray structural analysis reveals that complex 1 features a two-dimensional(2D) framework with 6~3-hcb topology. Moreover, the photoluminescent property of 1 was also discussed.     

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, [Zn2L2Cl4]·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-me- thylphenylimino)methyl]-6-methoxyphenol (C15H15NO2, 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, 1H-NMR spectra and thermogravimetric 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,Structure and Luminescent Properties of a Two-dimensional Cobalt(Ⅱ) Coordination Polymer Based on 2-Thiobarbituric Acid

A two-dimensional coordination polymer [Co(H_2tba)_2(DMF)_2]_n 1(H_2tba = 2-thiobarbituric acid anion, DMF = N,N-dimethylformamide) has been synthesized by Co Cl2·6H2O with the 2-thiobarbituric acid ligands under solvothermal conditions. Compound 1 was further characterized by FTIR, elemental analysis, TGA and powder XRD techniques. Single-crystal X-ray diffraction studies revealed that the title compound crystallizes in the monoclinic space group Pbca with a = 12.5948(12), b = 11.4269(11), c = 14.8939(15) ?, V = 2143.5(4) ?~3, Z = 4, Dc = 1.523 g·cm-3, F(000) = 1012, μ = 1.038 mm~(-1), R = 0.0358 and w R2 = 0.0888(I 2σ(I)). Single-crystal X-ray diffraction analysis reveals that 1 is the first two-dimensional noninterpenetrating(4, 4) net coordination polymer based on the 2-thiobarbituric acid. Coordination polymer 1 exhibits two luminescent emission spectra at 477 and 489 nm with the excitation peak at 273 nm.     

Three New Zn(Ⅱ) Coordination Compounds Based on the in-situ Formed Tetrazolate Ligand: Syntheses,Crystal Structures and Luminescence Properties

Reactions of 2-(2-benzoimidazolyl)acetonitrile and Na N3 with Zn SO4 or Zn Cl2 in the presence of nicotinic acid in the mixture of Et OH/H2 O afforded a mononuclear compound [Zn(L1)2](1) and a 1-D polymer [Zn(L1)Cl]n(2), respectively(L1 = 5-[(benzoimidazolyl)methyl]-1H-tetrazolate). However, in the similar condition except that imidazole was added instead of nicotinic acid, the reaction afforded a 1-D compound [Zn(L1)2]n(3) featuring triply helical chains via the π-π stacking of ligands. They are characterized by elemental analysis and IR, and their structures have been determined by X-ray crystallography. Thermal stability of these compounds was measured by TGA and their luminescent properties were investigated at room temperature.     

Solvothermal Synthesis and Crystal Structure of a Zn（II） Microporous Metal-organic Framework

A novel three-dimensional Zn(Ⅱ) coordination polymer, Zn3(C2H2N3)4(SiF6), has been synthesized under solvothermal conditions using 1H-1,2,4-triazole-3-carboxylic acid and zinc fluoride as the starting materials. The complex has been characterized by elemental analysis, IR, TG analysis and single-crystal X-ray diffraction analysis. The complex crystallizes in the tetragonal I4/mmm space group with a=11.592(0), c=7.526(1), V=1011.3(2)3 , Z=2, Mr=610.46, Dc=2.005 g/cm3 and F(000)=596. The final R=0.0312 and wR=0.067 for 319 observed reflections with I>2σ(I). In the title complex, the Zn centers are interconnected by μ 3 -bridging triazole ligands to form a microporous three-dimensional metal-organic framework.     

Synthesis, Crystal Structure and Magnetic Properties of a New Zn(Ⅱ)-Nitronyl Nitroxide Complex

A new complex [Zn(NIT-1'-MeBzIm)Cl2(H2O)] (NIT-1'-MeBzIm = 2-{2'-[(1'-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide) has been prepared and structurally characterized by X-ray diffraction method. Crystal data: monoclinic, space group P21/n, Z = 4, C15H21Cl2N4O3Zn, Mr = 441.63, a = 7.2225(10), b = 30.849(4), c = 8.8758(13) (A), β= 103.904(2)°, V = 1919.6(5) A3, Dc = 1.528 g/cm3, μ(MoKα) = 1.579 mm-1, F(000) = 908, R = 0.0436 and wR = 0.1029 for 2456 observed reflections with Ⅰ> 2σ(Ⅰ). X-ray analysis reveals that the Zn(Ⅱ) ion is four-coordinated with a distorted tetrahedron. There also exist H-bonds, π-π piling interactions and weak intermolecular contacts between the NO groups which form a mutual stagger 3-D network configuration. Magnetic investigation reveals that there exists intermolecular antiferro- and ferromagnetic interactions in the title complex.     

Synthesis, Crystal Structure and Magnetic Properties of a New Zn(II)-Nitronyl Nitroxide Complex

A new complex [Zn(NIT-1'-MeBzIm)Cl2(H2O)] (NIT-1'-MeBzIm = 2-{2'-[(l'- methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been prepared and structurally characterized by X-ray diffraction method. Crystal data: monoclinic, space group P21/n, Z = 4, C15H21Cl2N4O3Zn, Mr = 441.63, a = 7.2225(10), b = 30.849(4), c = 8.8758(13) , β = 103.904(2)°, V = 1919.6(5) 3, Dc = 1.528 g/cm3, μ(MoKα) = 1.579 mm1, F(000) = 908, R = 0.0436 and wR = 0.1029 for 2456 observed reflections with I > 2σ(I). X-ray analysis reveals that the Zn(II) ion is four-coordinated with a distorted tetrahedron. There also exist H-bonds, π-π piling interactions and weak intermolecular contacts between the NO groups which form a mutual stagger 3-D network configuration. Magnetic investigation reveals that there exists intermolecular antiferro- and ferromagnetic interactions in the title complex.     

Synthesis,Crystal Structure,and Luminescence of a 1D Chain Cd(Ⅱ) Polymerwith 3,3?,5,5?-Benzene-1,3-biyl-tetrabenzoic Acid

A new Cd(Ⅱ) coordination polymer, [Cd(H_2btb)(bpy)]_n(1, H_4btb = 3,3?,5,5?-benzene-1,3-biyl-tetrabenzoic acid, bpy = 2,2?-bipyridine), has been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric(TG) analyses and single-crystal X-ray diffraction techniques. Complex 1 belongs to monoclinic system, C2/c space group. In 1, two carboxylate groups of the H_4btb ligand adopt bidentate chelating and μ_2-η~1:η~1 coordination modes, respectively, bridging the Cd(Ⅱ) atoms to generate a 1D polymeric ribbon. In addition, the photoluminescence property of complex 1 has also been studied.     

Hydrothermal in situ Ligand Synthesis from 1,10-Phenanthroline-5,6-dione and Characterization of 1D Coordination Polymers [Co（bpdc）（H2O）3] · H2O and [Cu（bpy）V2O6]

Hydrothermal treatment of MCl2(M=Co or Cu), NH4VO3, and 1,10-phenanthroline-5,6-dione(pdon) resulted in the formation of a duplex coordination polymer [Co(bpdc)(H2O)3]·H2O(bpdc=2,2′-bipyridine-3,3′-dicarboxylate) and a chain-like coordination polymer [Cu(bpy)V2O6](bpy=2,2′-bipyridine). X-ray single-crystal structural analysis shows that under hydrothermal conditions and in the presence of different transition metals, the organic reagent pdon was transformed in situ into bpdc and bpy, respectively. Mechanism of the in situ ligand synthesis reaction has been discussed.