Synthesis and Structure of 4—Nitrobenzaldehyde Thiosemicarbazone

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Synthesis and Structure of 2—Acetylthiophene Thiosemicarbazone

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Synthesis and Crystal Structure of a Mn(Ⅱ) Complex with Thiosemicarbazone Derivative of Pyridine-3-carbaldehyde Showing Unusual Coordination Mode of Tridentate Thiosemicarbazone

The title complex Mn(HL)4(NCS)2(CH3CH2OH)2 has been achieved via selfassembly by incorporating manganese(Ⅱ) into pyridine-3-carbaldehyde thiosemicarbazonate ligand,and characterized by elemental analysis and single-crystal X-ray diffraction study. The crystal crystallizes in triclinic, space group P1 with a = 8.896(2), b = 9.530(2), c = 14.520(4) (A), α =87.035(4), β= 88.112(4), γ= 69.434(4)°, V= 1150.9(5) (A)3, Z = 1, Mr = 984.17, Dc = 1.420 g/cm3,μ(MoKα) = 0.612 mm-1, F(000) = 511, the final R = 0.0574 and wR = 0.1547 for 2855 observed reflections with I ＞ 2σ(I). The complex contains one six-coordinated manganese ion connected by two thiosemicarbazide ligands, in which the thiosemicarbazone ligand acts as a monodentate ligand and coordinates to the center metal atoms via the pyridyl nitrogen atoms, two ethanol molecules and two isothiocyanic anions to give rise to a mononuclear structure. The coordination of a potentially tridentate thiosemicarbazone in manganese(Ⅱ) complex without using its sulfur and imine nitrogen sites is unusual. Hydrogen bonds existing in the complex link the different components to stabilize the crystal structure.     

Synthesis and Crystal Structure of a Mn(II) Complex with Thiosemicarbazone Derivative of Pyridine-3-carbaldehyde Showing Unusual Coordination Mode of Tridentate Thiosemicarbazone

1 INTRODUCTION Heterocyclic thiosemicarbazones as well as their metal complexes have been attracting considerable interest due to their biological activities, such as antiviral, antibacterial, antimalarial, antifungal, and antitumoral activities[1～5]. This prompted us to carry out structural studies of these complexes to provide a basis for understanding their behaviors in living systems. Although quite a number of investigations on the 2-heterocyclic thiosemicarbazones have ap- peared[6…     

Synthesis of New Thiazine and Thiosemicarbazone Derivatives from D-Xylose

Thioureas have strong antifungal activities1 and their antimicrobial and insecticidal properties have been documented for more than fifty years2. Recently thiourea derivatives have been reported to possess antitubercular, antithyroid and anticancer3 prope…     

Structure and Luminescence Property of a Hexanuclear Thiosemicarbazone Silver（I） Cluster

A new hexanuclear silver(I) compound containing thiosemicarbazones with groups of 1-naphthalene was synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analysis and fluorescence spectrum.The title compound crystallizes in monoclinic,space group P2 1 /c with a=16.101(4),b=24.855(7),c=14.492(4),β=109.730(5)°,V=5459(3)3,C 90 H 102 Ag 6 N 24 O 6 S 6,M r=2455.54,D c=1.494 g/cm 3,μ(MoKα)=1.228 mm-1,F(000)=2472,Z=2,the final R=0.0761 and wR=0.1507 for 5258 observed reflections (I > 2σ(I)).In the structure,the S atom of ligand L serves as a triply bridged chelator to connect the six silver atoms into a Ag 6 L 6 cluster.Luminescence investigation reveals that the compound exhibits two ligand-independent cluster-centered electron transfer bands and one ligand-dependent charge transfer band.     

Structure and Luminescence Property of a Hexanuclear Silver（Ⅰ） Cluster Containing Benzaldehyde Thiosemicarbazone

A new hexanuclear silver (I) compound 2 containing thiosemicarbazone with the group of benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in triclinic, space group P with a = 11.611(3), b = 15.610(5), c = 15.624(7) , α = 113.942(6), β = 104.520(6), γ = 104.230(4)°, V = 2304.1(14) 3, C60H77Ag6N22O4.5S6, Mr = 2018.02, Dc = 1.454 g/cm3, μ(MoKα) = 1.435 mm-1, F(000) = 1005, Z = 1, the final R = 0.0468 and wR = 0.1474 for 6608 observed reflections (I > 2σ(I)). In the structure, the S atom of the ligand L2 (L2 = benzaldehyde thiosemicarbazone) served as a triply bridged chelator to connect the six silver atoms into a Ag6L26 cluster. The luminescence property of compound 2 was investigated at room temperature.     

Metal 2-Hydroxy-1-Naphthaldehyde Thiosemicarbazone (Me-HNT) Complexes-A New Kind of Biomimic Enzyme Catalyst

Enzymes have been widely used in analytical biochemistry and have considerableadvantages of rapidity and high selectivity'-', but they are expensive and their solutions arequite unstable. So study of biomimic enzyme become an important branch of enzyme,analysis'-'. Metal complexes are important mimetic resources, e-g. the metalloporphyrins.(MPs) system has been used as the model of mimic peroxidase'. As common ligands,Schiffbases are easy to be synthesized, dissolved and are widely used in me…     

Structure and Luminescence Property of a Hexanuclear Silver（I） Cluster Containing Pyridine-3-carboxaldehyde Thiosemicarbazone

A new hexanuclear silver(I) compound containing thiosemicarbazone with group of 3-pyridine was synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analysis and fluorescence spectrum.The title compound 3 crystallizes in monoclinic,space group C2/m with a = 18.6523(9),b = 24.7519(11),c = 22.4542(15) ,β = 93.4960(10)°,V = 10347.4(10)3,C68H104Ag6N30O8S6,Mr = 2309.39,Dc = 1.482g/cm3,μ(MoKα) = 1.293 mm-1,F(000) = 4656,Z = 4,the final R = 0.0544 and wR = 0.1580 for 6733 observed reflections(I > 2σ(I)).In the structure,two Ag6L36(L3 = pyridine-3-carboxaldehyde thiosemicarbazone) clusters are contained.In each cluster,the S atom of ligand L3 served as a triply bridged chelator to connect the six silver atoms into a Ag6L36 cluster.Luminescence investigation revealed that the band at 630 nm was attributed to cluster-centered(CC) electron transfer,and those at 493 and 530 nm to the LMCT and CC transitions,respectively.     

Synthesis, Structure and Comparison of Luminescent Property between Two Hexanuclear Silver（I） Thiosemicarbazone Clusters

A new silver(Ⅰ) compound 4 containing thiosemicarbazone with group 2-quinoline was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. Compound 4 crystallizes in triclinic, space group P1 with a = 12.2710(9), b = 16.9281(13), c = 17.2984(13), α = 112.8500(10), β = 103.4890(10), γ = 102.6860(10)°, V = 3020.9(4) 3, C80H94Ag6N28O6S6, Mr = 2383.41, Dc = 1.310 g/cm3, μ(MoKα) = 1.108 mm-1, F(000) = 1196, Z = 1, the final R = 0.0567 and wR = 0.1368 for 5112 observed reflections (I > 2σ(I)). Similar to the structure of compound 2 we have reported, compound 4 also exhibits a hexanuclear silver(Ⅰ) cluster. In the cluster, the S atom of ligand L4 (L4 = 2-quinolinecarboxaldehyde thiosemicarbazone) serves as a triply bridged chelator to connect the six silver atoms into a Ag6L46 cluster. The luminescence property of 4 is investigated at room temperature and compared with that of 2.     

Syntheses and Supramolecular Structures of Two Nickel(Ⅱ) Compounds Based on Two Thiosemicarbazone Ligands

Two new compounds, [Ni₂(L¹)(Py)₆]Py·CH₃OH(1) and [Ni₃(L²)₂(Py)₄]·2DMF(2)(H₄L¹=N,N'-bisalicyl- bisthiocarbamide; H₃L²=3-hydroxyl-2-naphthalene thiosemicarbazide; Py=pyridine; DMF=dimethyl fumarate), based upon two thiosemicarbazone ligands have been obtained and characterized by elemental analysis, Fourier transform infrared(FTIR) and X-ray diffraction(XRD). Compound 1 possesses a binuclear cluster, in which the bisalicylbisthiocarbamide acts as a hexadentate bridge. Compound 2 exhibits a linear trinuclear cluster with the triply-deprotonated ligand acting as pentadentate bridge. C―H···O, C―H···π and C―H···S weak interactions further link these molecules to form interesting supramolecular networks.     

Synthesis,Structure and Comparison of Luminescent Property between Two Hexanuclear Silver(Ⅰ) Thiosemicarbazone Clusters

A new silver(Ⅰ) compound 4 containing thiosemicarbazone with group 2-quinoline was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. Compound 4 crystallizes in triclinic, space group P1 with a = 12.2710(9), b = 16.9281(13), c = 17.2984(13), α = 112.8500(10), β = 103.4890(10), γ = 102.6860(10)°, V = 3020.9(4) 3, C80H94Ag6N28O6S6, Mr = 2383.41, Dc = 1.310 g/cm3, μ(MoKα) = 1.108 mm-1, F(000) = 1196, Z = 1, the final R = 0.0567 and wR = 0.1368 for 5112 observed reflections (I 2σ(I)). Similar to the structure of compound 2 we have reported, compound 4 also exhibits a hexanuclear silver(Ⅰ) cluster. In the cluster, the S atom of ligand L4 (L4 = 2-quinolinecarboxaldehyde thiosemicarbazone) serves as a triply bridged chelator to connect the six silver atoms into a Ag6L46 cluster. The luminescence property of 4 is investigated at room temperature and compared with that of 2.     

Antitumor Metallothiosemicarbazonate:Synthesis,Crystal Structure,Spectra and Antitumor Studies of Co(Ⅲ) Complex with Thiosemicarbazone Derivative of 2-Benzoylpyridine

The title complex Co(L)2Cl·4H2O I has been achieved via self-assembly by incorporating cobalt into 2-benzoylpyridine thiosemicarbazonate ligand, and characterized by elemental analysis, infrared spectra, mass spectra and single-crystal X-ray diffraction study. The crystal crystallizes in monoclinic, space group P21/n, with a=10.227(3), b=17.363(4), c=17.459(4), β=100.408(4)o, V=3049.2(13)3, Z=4, Mr=677.08, Dc=1.475 g/cm3, μ(MoKα)=0.834 mm-1, F(000)=1400, the final R=0.0747 and wR=0.0896 for 1663 observed reflections with I > 2σ(I). The complex contains one six-coordinated cobalt ion connected by two thiosemicarbazone ligands which act as a tridentate ligand to coordinate with the center metal atoms via two pyridyl nitrogen atoms, two imine nitrogen atoms and two sulfur atoms giving rise to a mononuclear structure. Hydrogen bonds existing in the complex link the different com-ponents to stabilize the crystal structure. The antitumor activity of the title complex was tested against A549 lung cancer cell line. Complex I exhibits antitumor activity.     

Antitumor Metallothiosemicarbazonate： Synthesis,Crystal Structure,Spectra and Antitumor Studies of Co（Ⅲ） Complex with Thiosemicarbazone Derivative of 2-Benzoylpyridine

The title complex [Co（L）2]Cl·4H2O I has been achieved via self-assembly by incorporating cobalt into 2-benzoylpyridine thiosemicarbazonate ligand, and characterized by elemental analysis, infrared spectra, mass spectra and single-crystal X-ray diffraction study. The crystal crystallizes in monoclinic, space group P2 1/n, with a = 10.227（3）, b = 17.363（4）, c = 17.459（4） A, β= 100.408（4）°, V= 3049.2（13） A^3, Z = 4, Mr = 677.08, Dc = 1.475 g/cm^3, μ（MoKα） = 0.834 mm^-1, F（000） = 1400, the final R = 0.0747 and wR = 0.0896 for 1663 observed reflections with I 〉 2σ（I）. The complex contains one six-coordinated cobalt ion connected by two thiosemicarbazone ligands which act as a tridentate ligand to coordinate with the center metal atoms via two pyridyl nitrogen atoms, two imine nitrogen atoms and two sulfur atoms giving rise to a mononuclear structure. Hydrogen bonds existing in the complex link the different components to stabilize the crystal structure. The antiturnor activity of the title complex was tested against A549 lung cancer cell line. Complex ! exhibits antitumor activity.     

Antitumor Comparison of Three α-N-Heterocyclic Thiosemicarbazone Derivatives' Crystal Structures of Bis(2-acetylpyridine)thiocarbonohydrazone and Bis(imidazole-2-carboxaldehyde)thiocarbonohydrazone

A series of ligands,HL1(2-acetylpyridine thiosemicarbazone),H2L2(bis(2-acetyl-pyridine) thiocarbonohydrazone) and H2L3(bis(imidazole-2-carboxaldehyde) thiocarbonohydrazone) was synthesized.H2L2 and H2L3 were characterized by elemental analysis,IR spectra and single-crystal X-ray diffraction studies.Hydrogen bonds link different components to stabilize the crystal structure in the two ligands.To comprehend the structure-activity relationship well,the three ligands are all tested against human K562 leucocythemia cell line with IC50 analysis.Different substituent groups on the ligands show different levels of antitumor activity.By comparison with the other species studied,H2L2 with thiocarbonohydrazone along with 2-acetylpyridine is the most active compound with IC50 = 2.48 μM.     

Crystal Structure,Electrochemical Properties and Third-order Nonlinear Optical Response of 4-Methyloxy benzaldehyde Thiosemicarbazone and Its Copper(Ⅱ)Complex

Thecurrentsurgeofinterestinthefield0fnon-linearoptics(NL0)isderivedbothfromaquestforafundamentalunderstanding0fthenon-linearprocess,anditSimPortanceinthetechn0logyofphotonics.Amongnon-linearphen0mena,thethird-ordernon-linearophcsoccuPyanimPortantp0sihonbecauseitprovidesthemechanicsforophcalswitching,ophcallogic,andreal-hmeholograPhy"'.0rganicmaterialwithextendednconjugahonsandlargeRdelocalizahonsarewellknownastheimPortantmaterialsofachievinglargethird-ordernonlinearihes3.ForexamPle,thiosen…     

New Copper（Ⅱ） and Nickel（Ⅱ） Complexes of 4-Morpholinoacetophenone Thiosemicarbazone： Structural, Electrochemical and Antimicrobial Studies

4-Morpholinoacetophenone thiosemicarbazone, MAPT, and its nickel（Ⅱ） and copper（Ⅱ） complexes have been prepared and characterized by elemental analysis, magnetic susceptibility, spectral methods （FT-IR, ^1H NMR） and cyclic voltammetry. Electrochemical behaviors of the complexes have been studied by cyclic voltammetry in DMF media showing metal centered reduction processes for both of them. The redox properties, nature of the electrode processes and the stability of the complexes were discussed. [Cu（MAPT）2]Cl2 complex shows Cu（Ⅱ）/Cu（Ⅰ） couple and quasi-reversible wave associated with the Cu（Ⅲ）/Cu（Ⅱ） process. The reduction/oxidation potential values depend on the structures of complexes. Also, the antimicrobial activities of these complexes were determined against S. aureus, E. coli and B. subtilis.     

Studies on the Effect of Various Anions and Pyridine on the Stereochemistry of Lanthanide(III) Coordination Compounds of 4[N-(2′-Hydroxy-1′-Naphthalidene)Amino] Antipyrine Thiosemicarbazone

In the present studies, the effect of pyridine on stereochemistry of the coordination compounds of lanthanide(III) derived from 4[N-(2′-hydroxy-1′-naphthalidene)amino] antipyrine thiosemicarbazone (HNAAPTS) has been studied. The general composition of the present complexes is LnX₃·n(HNAAPTS)·Py (Ln = La, Pr, Nd, Sm, Gd, Tb, Dy, or Ho; X = NO₃, n = 1, x = Cl, NCS or ClO₄, n = 2, Py = pyridine). All the complexes were characterized by elemental analyses, molecular weight, molar conductance, magnetic susceptibilities, infrared and electronic spectral studies. The infrared studies reveal that the HNAAPTS behaves as a neutral tridentate (N, N, S), while pyridine is coordinated to metal ions via its nitrogen atom. Nitrates are bicovalently bonded, while thiocyanate is coordinated through a strong N-atom. Perchlorate ions are not coordinating in coordination sphere. From electronic spectral data, nephelauxetic effect (β), covalence factor (b^½), Sinha parameter (δ%), and the covalence angular overlap parameter (η) have been calculated. Thermal stabilities of these complexes were studied by thermogravimetric analysis. In conclusion, the coordination number of lanthanides(III) in the present compounds is either seven or ten depending on the coordinating anions.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Synthesis and Structure of 1.5Zn（phen）3·L·3NO3 Supramolecule （phen = o-Phenanthroline,L = 4-Aminoacetophenone Thiosemicarbazone）

A supramolecular framework, 1.5Zn（phen）3·L·3NO3 （C63H48Zn1.5N16O9S）, has been synthesized. The ligand L was synthesized by the condensation of p-aminoacetophenone with thiosemicarbazide. The crystal belongs to the monoclinic system, space group C2/c, with a = 31.005（2）, b = 15.114（2）, c = 24.887（3） A, β = 94.260（2）° Z = 8, V = 11630（2）A^3 Dc = 1.489 g/cm^3, Mr = 1303.29,λ（MoKa） = 0.71069 A,μ= 0.735 mm^-1, F（000） = 5368, Rint = 0.0699, R= 0.0505 and wR= 0.0707. Two independent Zn atoms are both coordinated by six N atoms from three phen ligands. π-π and C-H…π interactions among the L ligands and Zn（phen）3 cations, π-π and C-H...π interactions among the Zn（phen）3 cations and N-H...O hydrogen bonds among the L ligands and nitrate anions connect the whole structure into a 3-D supramolecular framework.