Tin(IV) Complexes of 1,5-Diphenylthiocarbazone and Thiosemicarbazide: Synthesis,X-Ray Characterization,and Biological Activity

Abstract

The reaction of Me₂SnCl₂ with dithizone or thiosemicarbazide produced two novel di-organotin derivatives in good yields, which were characterized by X-ray diffraction. The crystal structures show that the compounds present a distorted pentacoordinated tin(IV) metal center. The antimicrobial activity of the new compounds was studied against Gram-negative (Escherichia coli, Klebsiella pneumonia, Salmonella enteritidis) and Gram-positive (Staphylococcus aureus) bacteria, and the yeast Saccharomyces cerevisiae. It was observed that the coordination of tin metal has a pronounced effect on the microbial activities of the ligands. All the tin complexes have shown higher antimicrobial effect than the free ligands.

GRAPHICAL ABSTRACT     

New Dithiocarbamate Compounds from Organotin(IV)

Abstract

A series of new organotin(IV) dithiocarbamate compounds of type R_nSn (S₂CNR′R″)_4-n (n = 2, 3; R = dimethyl, dibutyl, diphenyl, triphenyl and tert-butyl; R′ = methyl, ethyl, benzyl; R″ = isopropyl, ethyl, ethanol) have been successfully synthesized. Elemental analysis showed that the percentage of the elements conformed to the general formula of these compounds. The important peaks of the infrared spectra for the stretching mode ν(C?N), ν(C?S), and v(Sn-S) for the compounds were observed in the area of 1440–1480 cm^?1, 940–1000 cm^?1, and 340–90 cm^?1, respectively. The ¹³C NMR spectra showed the most important peak for N¹³CS₂ chemical shifts were observed in the range 190–210 ppm. X-ray single crystal studies for several structures of these compounds showed that the chelating mode of the dithiocarbamate groups to the central tin atoms were either bidentate or anisobidentate.

GRAPHICAL ABSTRACT     

Organotin(IV) complexes with 2-hydroxynaphthaldehyde-N(4)-ethylthiosemicarbazone: Synthesis,characterization, and in vitro antibacterial activity

Four new organotin(IV) complexes with 2-hydroxynaphthaldehyde-N(4)-ethylthiosemicarbazone [(H₂DNET), (1)] of the type [MeSnCl(DNET] (2), [BuSnCl(DNET)] (3), [PhSnCl(DNET)] (4), and [Ph₂Sn(DNET] (5) have been synthesized by the direct reaction of H₂DNET (1) with organotin(IV) chloride(s) in the presence of potassium hydroxide in absolute methanol. All the compounds were characterized by elemental analyses, molar conductivity, UV-Vis, IR, ¹H, ¹³C, and ¹¹⁹Sn NMR spectral studies. The molecular structure of ligand (1) has been confirmed by X-ray single crystal diffraction. Spectroscopic data clearly suggested that Sn(IV) center is coordinated with the ONS tridentate ligand (H₂DNET) and exhibits a five-coordinate geometry in solution. Antibacterial studies were carried out in vitro against four bacterial strains. All organotin(IV) compounds (2–5) showed good activity against various bacteria but lower activity than the reference drug (Ciprofloxacin). The results demonstrate that organic groups attached to tin(IV) moiety have significant effect on their biological activities. Among them, diphenyltin(IV) derivative 5 exhibits significantly good activity than the other organotin(IV) derivatives (2–4).     

3-三氯锡基丙酸酯及其配合物的合成与结构表征

合成了4个新的3-三氯锡基丙酸酯Cl3SnCH2CH2COOR(R=环戊基，1；环己基，2 ；环戊甲基，3；环己甲基，4)，并通过其与二丁基亚砜(L^1)、2，2’-联吡啶 (L^2)、1，10-菲咯啉(L^3)的低热固相反应合成了6个相应的配合物 Cl3SnCH2CH2COOR·L(L=L^1,a;L^2,b;L^3,c).利用元素分析、红外光谱、核磁共振 对其结构进行了表征，并通过X射线单晶衍射测定了1和2的晶体结构，二者均为具 有分子内羰基氧原子配位的畸变三角双锥结构．1属于单斜品系，空间群P21/c, a=0.9842(2)nm,b=1.0923(8)nm,c=1.23948(11)nm,β=93.894(15)°,V=1.3294(4) nm^3,Mr=366.23,Z=4.2属于单斜晶系，空间群P21/c,a=1.04443(9)nm,b=1.04823 (7)nm,c=1.28113(9)nm,β=90.953(8)°,V=1.40239(19)nm^3,Mr=380.25,Z=4.     

二正丁基锡水杨醛缩对氨基苯甲酸酯配合物的合成、表征及结构研究

The title complex {[ⁿBu₂Sn(2-OHC₆H₄CH=NC₆H₄COO)]₂O}₂·2H₂O was synthesized by the reaction of N-(4-carboxyphenyl)-salicylideneimine with dibutyltin(IV) oxide in 1∶1 molar ratio. The compound has been characterized by elemental analysis, IR, ¹H NMR spectra and X-ray single crystal diffraction. It crystallizes in triclinic system with space group P1. The crystal data are: a=1.242 9(2) nm, b=1.261 3(2) nm, c=1.594 9(3) nm, α=102.06(2)°, β=92.884(3)°, γ=95.939(3)°, Z=2, D_c=1.342 g·cm^-3, F(000)=1 000, V=2.425 2(7) nm³, R₁=0.041 5, wR₂=0.104 4. The compound is in centro-symmetric dimer structure mode with a four-member central endo-cyclic Sn₂O₂ unit in which the bridging oxygen atoms are tri-coordinated. All the tin atoms are five-coordinated with geometry of distorted trigonal bipyramid. CCDC:286105.     

Synthesis,spectroscopic characterization,crystal structure,and anti-bacterial activity of diorganotin(IV) complexes with 5-bromo-2-hydroxybenzaldehyde-N(4)-ethylthiosemicarbazone

Three new diorganotin(IV) complexes, [Me₂Sn(BDET] (2), [Bu₂Sn(BDET)] (3), and [Ph₂Sn(BDET)] (4), were synthesized by reacting R₂SnCl₂ (R = Me, Bu, and Ph) with 5-bromo-2-hydroxybenzaldehyde-N(4)-ethylthiosemicarbazone [H₂BDET, (1)] in the presence of KOH in absolute methanol. The newly synthesized complexes were characterized by elemental analysis, molar conductivity, UV–vis, FT-IR, ¹H, ¹³C, and ¹¹⁹Sn NMR spectroscopies. The molecular structure of 4 was confirmed by X-ray crystallography. X-ray crystallography revealed that the doubly deprotonated O,N,S-tridentate thiosemicarbazone coordinates to tin(IV), resulting in a distorted trigonal bipyramidal geometry. Their ¹H, ¹³C, and ¹¹⁹Sn NMR spectra support a five-coordinate tin(IV) in solution for all complexes, in accord with the solid-state X-ray structure determined for 4. Compounds 1–4 were evaluated for their antibacterial activities against Staphylococcus aureus, Enterobacter aerogenes, Escherichia coli, and Salmonella typhi. The results exhibited that 2–4 were active with comparable potency compared to the standard drug. Antibacterial studies also indicated that the complexes have potential for biological evaluation.     

Structural Studies on Dimethyltin(IV) Carboxylates

In order to correlate ¹¹⁹Sn Mössbauer parameters and structural data for dimethyltin(IV) derivatives, the molecular structures of bis(acetato)dimethyltin(IV) and bis(trifluoroacetato)dimethyltin(IV) were determined by single crystal X-ray diffration. Crystals of Me₂Sn(OOCCH₃)₂ are monoclinic, a = 26.282(4), b = 5.282(1), c = 14.434(3) Å, β = 101.17(2)°, Z = 8, space group C2/c, and those of [Me₂Sn(OOCCF₃)₂]_n are monoclinic, a = 8.444(1), b = 17.689(1), c = 15.368(1) Å, β = 93.013(9)°, Z = 8, space group Cc. The structures were solved by the Patterson method and were refined by full-matrix least-squares procedures to R = 0.025 and 0.027 (R_w = 0.023 and 0.030) for 2 298 and 4 182 reflections with I ≥ 3σ(F²), respectively.     

Synthesis, Spectroscopic Properties and Crystal Structures of Dibenzyltin（IV） Dithiobenzoate and Chlorodibenzyltin（IV） Thiobenzoate

Two dibenzyltin(IV) complexes with thiobenzoate ligand, (PhCH2)2Sn(SOCPh)2 (1) and (PhCH2)2Sn(C1)SOCPh (2), have been synthesized by the reaction of dibenzyltin(IV) dichloride with thiobenzoic acid in the presence of organic base Et3N and characterized by IR, ^1H NMR spectroscopy and elemental analysis. Their crystal structures were determined by X-ray single crystal diffraction analysis. In the crystals of 1, the tin atom is six-coordinated in a distorted octahedron configuration. In the crystals of 2, the molecular packing in unit cell reveals that the two adjacent molecules are symmetrically linked to each other to form a dimer with intermolecular Sn…C1 distances of 0.3591 (2) nm and the tin atom is five-coordinated in a distorted trigonal bipyramid configuration.     

Synthesis,Characterization, Thermal,and Antibacterial Studies of Organotin(Iv) Complexes of Indole-3-Butyric Acid and Indole-3-Propionic Acid

Abstract

Six organotin(IV) complexes of type Me₂SnL₂, Bu₂SnL₂, and Ph₃SnL [where L = indole-3-butyric acid (1, 2 and 3) or indole-3-propionic acid (4, 5 and 6)] have been synthesized by the reactions of the corresponding diorganotin(IV) oxide and triphenyltin(IV) hydroxide with respective indole-3-butyric acid (IBH) or indole-3-propionic acid (IPH) in the desired molar ratios of 1:2/1:1. All of the compounds have been characterized by elemental analysis, IR, ¹H NMR, ¹³C NMR, and ¹¹⁹Sn NMR spectroscopy. Thermal studies of all synthesized complexes have been carried out using thermogravimetry (TG) technique under a nitrogen atmosphere. The thermal decompositions for compounds Me₂SnL₂ and Bu₂SnL₂ occurred in two steps, whereas in compounds Ph₃SnL, it exhibited as three steps decomposition and resulted into the formation of pure SnO₂. The complexes were also screened against three gram-positive (Staphylococcus aureus, Staphylococcus epidermidis, and Micrococcus luteus) and three gram-negative (Escherichia coli, Pseudomonas aeruginosa, and Enterobacter aerogenes) bacteria using minimum inhibition concentration (MIC) method, and all of these complexes showed significant antibacterial activity.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional text, tables, and figures.]     

Synthesis, Characterization and Properties of Organotin Complexes Dibutyltin（Ⅳ） Bis（heteroaromatic carboxylate） and Crystal Structure of Dibutyltin（Ⅳ） Bis（2-thiazolylcarboxylate）

The six organotin complexes dibutyltin(IV) bis(heteroaromatic carboxylate) were synthesized by the reaction of (n‐Bu)2SnO with heteroaromatic carboxylic acid in 1:2 molar ratio. These complexes have been characterized by elemental analysis, IR, ¹H, ¹³C and ¹¹⁹Sn NMR. The crystal structure of dibutyltin(IV) bis(2‐thiazolylcarboxylate) was determined by X‐ray single crystal diffraction. This compound is a weakly bridged dimer through weak interaction Sn···O between molecules. The tin atoms took six‐coordinate skew‐trapezoidal bipyramidal geometry. The crystal of complex 3 belongs to monoclinic symmetry with space group P2₁/c, a=1.863(2) nm, b=2.220(3) nm, c=1.0395(10) nm, β=90.275(16)°, Z=8, V=4.292(8) nm³, D_c=1.514 Mg/m³, μ=1.406 mm^‐1, F(000)=1968, S=0.999, R=0.0549, wR=0.1011.     

A chiral Mn(IV) complex and its supramolecular assembly: Synthesis, characterization and properties

The open air reaction of the chiral Schiff base ligand H₂L, prepared by the condensation of L-phenylalaninol and 5-bromosalicylaldehyde, with Mn^II(CH₃COO)₂.4H₂O yielded dark brown complex [Mn^IV L₂]·0·5 DMF (1). Compound 1 was characterized by elemental analysis, IR, UV-visible, CD and EPR spectroscopy, cyclic voltammetry and room temperature magnetic moment determination. Single-crystal X-ray analysis revealed that compound 1 crystallises in the monoclinicP2 ₁ space group with six mononuclear [Mn^IV L₂] units in the asymmetric unit along with three solvent DMF molecules. In the crystal structure, each Mn(IV) complex, acting as the building unit, undergoes supramolecular linking through C-H...0 bonds leading to an intricate hydrogen bonding network.     

Organotin(IV) carboxylates of cyclopropane carboxylic acid and 3‐cyclohexylpropanoic acid: synthesis,characterization and biological activity. The crystal structure of bis(cyclopropanecarboxylato) tetramethyldistannoxane

A series of tri‐ and di‐organotin(IV) derivatives of the types R₃SnL, R₂SnL₂ and [(R₂SnL)₂O]₂ have been synthesized by the reaction of tri‐ and di‐organotin(IV) chloride(s) with sodium cyclopropane carboxylate and sodium 3‐cyclohexylpropanoate. Based on spectroscopic evidence (IR and NMR), all the triorganotin carboxylates were found to be penta‐coordinated in the solid state (except the tricyclohexyltin derivative, which was found to be four‐coordinated) and four‐coordinated in the solution state. Attempted reaction of Me₂SnCl₂ with sodium cyclopropane carboxylate in 1:2 stoichiometry afforded a bis(dicarboxylato tetraorganodistannoxane) complex, {[Me₂Sn(cyclo‐CH₂)₂CHCOO]₂O}₂. The X‐ray diffraction of this ‘dimethyltin(IV) complex’ shows that the compound possesses a tetranuclear aggregate with one bridging bidentate and other free organic ester type monodentate carboxylate groups in which each Sn atom has a five‐coordinated geometry. These complexes were also screened for their antifungal activities. Copyright © 2008 John Wiley & Sons, Ltd.     

两个有机锡呋喃-2-甲酸酯化合物的合成、结构及量子化学研究

氧化双[三(2-甲基-2-苯基)丙基锡]、三苄基氯化锡分别与呋喃-2-甲酸反应,合成了配位聚合物{[(C4H3O)CO2]Sn(CH2CPhMe2)3}n(1)和{[(C4H3O)CO2]Sn(CH2Ph)3}n(2)。经IR、1H NMR、元素分析和X射线衍射表征结构。1和2均属单斜晶系,配合物1空间群P21/n,晶体学参数:a=1.122 06(7)nm,b=1.747 60(11)nm,c=1.632 62(10)nm,β=91.503(3)°,Z=4,V=3.200 3(3)nm3,Dc=1.306 g.cm-3,μ(Mo Kα)=0.829 mm-1,F(000)=1 304,R1=0.023 9,wR2=0.059 4。配合物2空间群C2/c,晶体学参数:a=2.939 49(13)nm,b=1.035 36(4)nm,c=1.976 64(9)nm,β=129.582(2)°,Z=8,V=4.636 4(3)nm3,Dc=1.442 g.cm-3,μ(Mo Kα)=1.125 mm-1,F(000)=2 032,R1=0.024 2,wR2=0.060 6。配合物1和2的中心锡原子分别为四面体和三角双锥构型。通过分子间氢键作用,1和2分别形成三维结构。对配合物进行了量子化学从头计算,探讨了配合物的稳定性、分子轨道能量及一些前沿分子轨道的组成特征。     

Synthesis and Structure of bc-Dichloro-af-dihydroxo-de-bis（N-3- pyridinylmethanesulfonamide）platinum（IV） Diydrate

The Pt(IV) complex cis,cis,trans-[Pt(PMSA)2Cl2(OH)2]·2H2O(1), where PMSA = N-3-pyridinylmethanesulfonamide, has been synthesized and characterized by elemental analysis, molar electric conductivity and...     

草酰胺桥联异三核配合物Cu(NiL)2(ClO4)2的合成、光谱表征和晶体结构(英)

A novel oxamido-bridged trinuclear complex Cu(NiL)₂(ClO₄)₂(where H₂L=2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,3-dien) has been synthesized and characterized by elemental analysis, IR spectrum, UV-Visible spectrum and single crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P2₁/n. The lattice parameters are: a=1.052 4(6) nm, b=1.182 1(6) nm, c=1.586 2(9) nm, β=91.657(9)°, and V=1.972 6(19) nm³, Z=2. The results show that the coordination geometry around copper(Ⅱ) in the title complex is hexa-coordinated octahedron. CCDC: 232608.     

meso-四(对烷氧基苯基)卟啉配合物的合成、表征和液晶性研究

The method of Adler was improved to prepare a series of 5,10,15,20-tetrakis(4-alkoxyphenyl)porphyrins and their complexes containing Fe³⁺, Mn³⁺, Pb²⁺, Co²⁺, Cu²⁺, Zn²⁺. Among them there were seven new compounds. All these compounds were identified through ¹H NMR, MS, IR, UV and Element analysis. The correlation between the structure of compounds and their ¹H NMR, MS, IR, UV spectra was discussed and their specific spectra were explained. We found nine metalloporphyrins exhibited liquid crystal behaviour through DSC and polarized-light microscope. They had one to three mesophases and certain phase transition temperature, ΔH and temperature range of L.C(ΔT).