New di‐ and triorganotin(IV) carboxylates derived from a Schiff base: synthesis,characterization and in vitro antimicrobial activities

A new carboxylic acid, 2‐{[5‐(2‐nitrophenyl)furan‐2‐yl]methyleneamino}benzoic acid (HOBZ), has been produced by reacting 5‐(2‐nitrophenyl)furfural with 2‐aminobenzoic acid. Reactions of NaOBZ with organotin chlorides led to formation of [Me₃Sn(OBZ)] ( 1 ), [Bu₃Sn(OBZ)] ( 2 ), [Me₂Sn(OBZ)₂] ( 3 ) and [Bu₂Sn(OBZ)₂] ( 4 ). Complexes 1 , 2 , 3 , 4 have been characterized using elemental analyses and infrared, ¹H NMR, ¹³C NMR, ¹¹⁹Sn NMR and ¹¹⁹Sn Mössbauer spectroscopies. In the solid state, the OBZ ligands might coordinate to tin in an anisobidentate fashion via the carboxylate group. The in vitro antimicrobial activity of all compounds has been screened against the following fungi: Aspergillus niger, A. flavus, A. parasiticus, Penicillium citrinum, Candida dubliniensis, C. lusitaniae, C. albicans, C. tropicalis, C. parapsilosis and C. glabrata; and against the following bacteria: Staphylococcus aureus, Listeria monocytogenes, Bacillus cereus, Streptococcus sanguinis, Escherichia coli, Citrobacter frendii, Salmonella typhimurium and Pseudomonas aeruginosa. Complexes 2 and 4 exhibited higher biocide activity in comparison to 1 and 3 and to the control drugs nystatin and miconazole nitrate for the yeasts, and chloramphenicol and ampicillin for the bacteria. The biological activity of 2 was superior to that of 4 . In addition, the toxicity of HOBZ, NaOBz and 1 , 2 , 3 , 4 were determined using Chlorella vulgaris, revealing low toxicity of the complexes at MIC₅₀ concentrations. We also performed cell viability studies, using XTT assay, displaying no change in the mitochondrial function after 2–4 h of exposure of the microorganism to the complexes at MIC₅₀ concentrations. The butyl‐containing complexes 2 and 4 display greater lipophilicities than do the methyl analogues 1 and 3 , thereby endowing 2 and 4 with superior abilities to cross the microbe cell membrane, the possible mechanism of action. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

双(三烃基锡)二元羧酸酯的合成、结构和农药活性普筛

合成了一系列双(三烃基锡)二元羧酸酯类化合物,表征了这些化合物的结构,并进行了农药活性普筛。结果表明,三环己基锡系列大多具有很好的杀螨和杀虫活性,三苯基锡系列则在除草和植物生物刺激方面有一定效果。同时,还发现农药活性同二元羧酸酯的骨架有关,邻苯二甲酸和丁烯二酸衍生物的效果优于脂肪二酸衍生物。     

Synthesis of new phosphorus ylides: Spectroscopic and X‐ray structural studies

Stable phosphoranes, Ar₃P = CHCOR (R = C₆H₅, C₆H₄NO₂, C₆H₄OCH₃, CH₃, OCH₂C₆H₅; Ar = p‐tolyl or phenyl), have been C‐acylated by acetic anhydride to obtain new types of phosphorus ylides. Synthesis and characterization of six phosphorus ylides of the type Ar₃PC(COCH₃)(COR) are reported. The reaction of {(p‐tolyl)₃PCHCOC₆H₅} ( I ), {(p‐ tolyl)₃PCHCOC₆H₄NO₂} ( II ), {Ph₃PCHCOC₆H₄NO₂} ( III ), {Ph₃PCHCOC₆H₄OCH₃} ( IV ), {(p‐tolyl)₃PCHCOCH₃} ( V ), and {Ph₃PCHCOOCH₂C₆H₅} ( VI ) with acetic anhydride in dry chloroform as solvent gives (p‐tolyl)₃PC(COMe)(COC₆H₅), α‐acetyl‐α‐benzoylmethy‐lenetriphenylphosphorane ( 1 ), {(p‐tolyl)₃PC(COMe) (COC₆H₄NO₂)} ( 2 ), {Ph₃PC(COMe)(COC₆H₄NO₂)} ( 3 ), {Ph₃PC(COMe)(COC₆H₄OCH₃)} ( 4 ), {(p‐tolyl)₃ PC(COCH₃)₂} ( 5 ), and {Ph₃PC(COMe)(COOCH₂ C₆H₅)} ( 6 ). Single crystal X‐ray analyses for ylides 2 , 5 , and 6 reveal the monoclinic ( 2, 5 ) and triclinic ( 6 ) crystal systems. Characterization of the obtained compounds was also performed by elemental analysis, IR, ¹H, ³¹P, and ¹³C NMR. The geometries of these compounds have been investigated using density functional theory (DFT). In addition, electronic parameters of these compounds such as HOMO and LUMO energy, Mulliken partial charge, and dipole moment were obtained. In this paper, the reactivity of these ylides is discussed in regard to the aforementioned data. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:475–485, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20633     

Review: structural diversity in organotin(IV) dithiocarboxylates and carboxylates

Organotin(IV) complexes are known for their outstanding structural diversity and applications. Organotin(IV) carboxylates and dithiocarboxylates form an important class of organotin(IV) compounds. The structural diversity of these compounds emanates from several features including flexibility in coordination geometries, coordination numbers, and versatility of the ligands to engage in different modes of chelation from monodentate to bidentate. Triorganotin(IV) complexes with various ligands mostly demonstrate tetrahedral or trigonal bipyramidal symmetry with some distortions, while diorganotin(IV) and chlorodiorganotin(IV) complexes have variation of geometries and coordination numbers. Some monoorganotin(IV) complexes have also been reported with pentagonal bipyramidal geometries.     

Antimicrobial activity of organotin(IV) compounds: a review

A comprehensive review on antimicrobial activity of organotin(IV) compounds is presented. Copyright © 2008 John Wiley & Sons, Ltd.     

Germanium carboxylates: the first X‐ray diffraction study of germanium(II) dicarboxylate and germanium(IV) tetracarboxylate

Germanium(II) dipropionate (1) has been synthesized and its crystal structure, as well as that of germanium(IV) tetrapropionate (2), has been determined. By contrast to monomeric 2 with monodentate propionate ligands, compound 1 is associated, forming a cyclotetramer [Ge(O₂CEt)₂]₄ (1a) via intermolecular dative C?O → Ge interactions. Copyright © 2005 John Wiley & Sons, Ltd.     

Syntheses,structural characteristics,and antimicrobial activities of new organotin(IV) 3-(4-bromophenyl)-2-ethylacrylates

New organotin(IV) carboxylates, [n-Bu₂SnL₂] (1), [Et₂SnL₂] (2), [Me₂SnL₂] (3), [n-Oct₂SnL₂] (4), [n-Bu₃SnL] _n (5), [Me₃SnL] _n (6), and [Ph₃SnL] _n (7), where L?=?3-(4-bromophenyl)-2-ethylacrylate, were synthesized and characterized by elemental analysis, FT-IR, and multinuclear NMR (¹H, ¹³C, and ¹¹⁹Sn). Spectroscopic studies confirm coordination of L to the organotin moiety via COO group. Single-crystal X-ray analysis reveals bridging mode of coordination in 6. Packing diagram established a supramolecular cage-like structure for 6 due to Sn–O interactions (3.287?Å). Subsequent antimicrobial activities proved them to be active biologically.     

Synthesis,characterization and biological activity of a novel binuclear organotin complex,Ph3Sn(HL)·Ph2SnL [L = 3,5‐Br2‐2‐OC6H2CHNCH(i‐Pr)COO]

A 1:1 reaction of triphenyltin chloride with potassium N‐[(3,5‐dibromo‐2‐hydroxyphenyl)methylene] valinate in benzene under reflux leads to the formation of a novel mixed organotin binuclear complex, Ph₃Sn(HL)·Ph₂SnL [L = 3,5‐Br₂‐2‐OC₆H₂CH?NCH(i‐Pr)COO], by means of a facile phenyl–tin bond cleavage process. The X‐ray structure reveals that there are two distinct types of carboxylate coordination mode and trans‐O₂SnC₂N and trans‐O₂SnC₃ in distorted trigonal bipyramidal geometries. The complex displays good in vitro cytotoxicity and antibacterial activities. Copyright © 2005 John Wiley & Sons, Ltd.     

Preparation,spectroscopic investigation and antibacterial activity of some organomercury(II) and organotin(IV) dithio complexes

Phenylmercuric acetate, triphenyltin chloride and dibutyltin chloride react with alkali‐metal or ammonium salts of some 1,1‐ and 1,2‐dithio ligands in appropriate molar ratios to yield a series of organometallic dithio complexes of the type [PhHgX] (X = butylxanthate (Buxant⁻), cyclohexylxanthate (Cyxant⁻), benzylxanthate (Bzxant⁻) or pyrrolidin‐1‐yldithiocarbamate (Pdtc⁻); [(PhHg)₂X] (X = isomaleonitriledithiolate (i‐MNT²⁻) or 1‐ethoxycarbonyl‐1‐cyanoethylene‐2,2‐dithiolate (ecda²⁻); Ph₃SnX (X = Buxant⁻ or Pdtc⁻); [(Ph₃Sn)₂(i‐MNT)] and [Bu₂SnMNT] (MNT²⁻ = maleonitriledithiolate). These complexes have been characterized by elemental analysis, molar conductance measurements, IR, FT‐Raman, ¹H and ¹³C NMR and fast atom bombardment (FAB) mass spectra. Cyclic dimeric structures for phenylmercuryxanthates and monomeric structures for the remaining complexes are suggested. Antibacterial activities of the complexes and parent ligands have been screened against some well‐known pathogenic bacteria. Organomercury dithiolates have been found to be more potential antibacterial than organotin complexes. Copyright © 2000 John Wiley & Sons, Ltd.     

Synthesis and structural characterization of organotin(IV) carboxylates based on different heterocyclic substituents

Six novel organotin(IV) carboxylates have been successfully synthesized, namely, the polymer (C₆H₅)₃Sn(L1)_∞ (1) [HL1 = 4-imidazolyl benzoic acid], the mononuclear (C₆H₅)₃Sn(L2) (2) [HL2 = 4-pyrazolylbenzoic acid], (C₆H₅)₃Sn(L3)·CH₃OH (3) [HL3 = 4-triazolylbenzoic acid] and (C₆H₅)₃Sn(L4) (4) [HL4 = 4-tetrazolyl benzoic acid] and the tetranuclear [(n-Bu₂Sn)₄(L2)₂O₂(OCH₃)₂] (5) and [(n-Bu₂Sn)₄(L3)₂O₂(OCH₃)₂] (6). X-ray diffraction analyses show 1D infinite chain of polymer 1, single molecular structures of isomorphous complexes 2 and 4, single molecule structures of complex 3 containing solvent CH₃OH molecule and similar ladder-type structures of complexes 5 and 6. The photoluminescence of ligands and 1-6 were also measured in the solid state at room temperature.     

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.     

Synthesis,characterization, X‐ray crystal structure and in vitro antitumour activity of sodium bis(2‐(3′,6′,9′‐trioxadecyl)‐1,2‐dicarba‐closo‐dodecaborane‐1‐carboxylato)triphenylstannate

Sodium bis[2‐(3′,6′,9′‐trioxadecyl)‐1,2‐dicarba‐closo‐dodecaborane‐1‐carboxylato]triphenylstannate, [(CH₃OCH₂CH₂OCH₂CH₂OCH₂CH₂)‐1,2‐C₂B₁₀H₁₀‐9‐COO)₂SnPh₃]^? Na⁺, compound 1, was synthesized by the 1:1 condensation of triphenyltin(IV) hydroxide with 2‐(3′,6′,9′‐trioxadecyl)‐1,2‐dicarba‐closo‐dodecaborane‐1‐carboxylic acid and crystallized in the presence of sodium bicarbonate. Its structure was determined by spectroscopy, elemental analysis and X‐ray diffraction. The structure of 1 consists of trigonal bipyramidal [Sn(Ph)₃(L)₂]^? anions and Na⁺ cations coordinated by oxygen atoms of polyoxaalkyl chains of different stannate anions, forming cation–anion chains elongated along the c axis. Compound 1 is significantly more active in vitro against seven tumour cell lines of human origin than 5‐fluorouracil, cis‐platin, carboplatin, and previously reported organotin carboranecarboxylates, but is less active than organotin polyoxaalkylcarboxylates. Copyright © 2004 John Wiley & Sons, Ltd.     

S,N‐Chelated organotin(IV) compounds containing 6‐phenylpyridazine‐3‐thiolate ligand—structural,antibacterial and antifungal study

A series of tri‐ and diorganotin(IV) compounds containing potentially chelating S,N‐ligand(s) (L^SN, where L^SN is 6‐phenylpyridazine‐3‐thiolate) were prepared and structurally characterized by multinuclear NMR spectroscopy. X‐ray diffraction techniques were used for determination of the structure of compounds containing one [(L^SN)Ph₂SnCl], two [(n‐Bu)₂Sn(L^SN)₂] and the combination of two L^SN and one L^CN [(L^CN)(n‐Bu)Sn(L^SN)₂] (where L^CN is {2‐[(CH₃)₂NCH₂]C₆H₄}‐) ligands. The coordination number of the tin atom varies from five to seven and is dependent on the number of chelating ligands present. The formation of the five‐membered azastanna heterocycle is favored over the formation of four‐membered azastannathia heterocycle in compounds containing both types of ligands. The di‐n‐butyl‐substituted compounds are the most efficient ones in inhibition of growth of yeasts, molds and G⁺ bacteria strains. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and structural characterization of monomeric and polymeric supramolecular organotin(IV) 4-chlorophenylethanoates

Four monomeric [n-Bu₂SnL₂ (1), Et₂SnL₂ (2), Me₂SnL₂ (3), and n-Oct₂SnL₂ (7)] and three polymeric {[n-Bu₃SnL]_n (4), [Me₃SnL]_n (5), and [Ph₃SnL]_n (6)} organotin(IV) carboxylates, where L?=?4-chlorophenylethanoate, were synthesized and characterized by elemental analysis, FT-IR, and multinuclear NMR (¹H, ¹³C, and ¹¹⁹Sn). Compounds 2 and 5 were also analyzed by X-ray single-crystal analysis showing monomeric and zigzag structures, respectively. Two types of O…H (2.641?Å) and Cl…H (2.943?Å) non-covalent interactions generate a 2-D supramolecular structure for 2. Layer-by-layer supramolecular structure was observed for 5 in which polymeric chains are connected via non-covalent interactions {Cl…H (2.869?Å), H…π (2.899?Å)}, and unconventional dihydrogen {H…H (2.381?Å)} interactions.     

Di‐ and tri‐organotin derivatives of 3S,4S‐3‐[(R)‐1‐(tert‐butyl‐dimethylsilyloxy)ethyl]‐4‐[(R)‐1‐carboxyethyl]‐2‐azetidinone: synthesis,characterization and in vitro antitumour activity

Di‐n‐butyl‐, triphenyl and tri‐n‐butyltin derivatives of 3 S, 4 S ‐3‐[( R )‐1‐(tert‐butyldimethyl‐­<?tw=103.5%>silyloxy)ethyl‐4‐[( R )‐1‐carboxyethyl]‐2‐azetidi<?tw>‐­none were synthesized and characterized. Their antitumour activity was screened against seven tumoural cell lines of human origin. Copyright © 1999 John Wiley & Sons, Ltd.