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1.
The diorganotin(IV) dichlorides R2SnCl2 (R: Ph, PhCH2 or n‐Bu) react with 2‐mercapto‐6‐nitrobenzothiazole (MNBT) in benzene to give [Ph2SnCl(MNBT)] ( 1 ), [(PhCH2)2Sn(MNBT)2] ( 2 ) and [(n‐Bu)2Sn(MNBT)2] ( 3 ). The three complexes have been characterized by elemental analysis and IR, 1H, 13C and 119Sn NMR spectroscopies. X‐ray studies of the crystal structures of 1 , 2 and 3 show the following. The tin environment for complex 1 is distorted cis‐trigonal bipyramid with chlorine and nitrogen atoms in apical positions. The structure of complex 2 is a distorted octahedron with two benzyl groups in the axial sites. The geometry at the tin atom of complex 3 is that of an irregular octahedron. Interestingly, intra‐molecular non‐bonded Cl…S interactions and S…S interaction were recognized in the crystallographic structures of 1 and 3 respectively. As a result, complex 1 is a polymer and complex 3 is a dimer. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

2.
Five new diorganotin N‐[(3‐methoxy‐2‐oxyphenyl)methylene] tyrosinates, R2Sn[2‐O‐3‐MeOC6H3CH=NCH (CH2C6H4OH‐4)COO] (R = Me, 1 ; Et, 2 ; Bu, 3 ; Cy, 4 ; Ph, 5 ), have been synthesized and characterized by elemental analysis, IR, NMR (1H, 13C and 119Sn) spectra, and the X‐ray single crystal diffraction. In non‐coordinated solvent, complexes 1 – 5 have penta‐coordinated tin atom. In the solid state, 1 – 3 are centrosymmetric dimmers in which each tin atom is seven‐coordinated in a distorted pentagonal bipyramid, and 4 displays discrete molecular structure with distorted trigonal bipyramidal geometry, and the tin atom of 5 is hexa‐coordinated and possess the distorted octahedral geometry with a coordinational methanol molecule. The intermolecular O‐H???O hydrogen bonds in 1 – 4 link molecules into the different one‐dimensional supramolecular chain with R22 (30) or R22 (20) macrocycles, and the molecules of 5 are joined into a two‐dimensional supramolecular network containing R44 (24) and R44 (28) two macrocycles. Bioassay results against human tumour cell HeLa indicated that 3 ‐ 5 belonged to the efficient cytostatic agents and the activity decreased in the order 4 > 3 > 5 > 2 > 1. The fluorescence determinations show the complexes may be explored for potential luminescent materials.  相似文献   

3.
Four triorganotin(IV) complexes with 2‐mercaptopyrimidine (HSpym) and 4‐amino‐2‐mercaptopyrimidine (HSapym) of the type, R3SnL (L= Spym, R=Ph, 1; R=PhCH2, 2; L=Sapym, R=Ph, 3; R=PhCH2, 4), were synthesized. All the complexes 1–4 have been characterized by elemental, IR, 1H NMR, and X‐ray crystallography diffraction analyses, which revealed that the structures of 1–4 are penta‐coordinated with R3Sn‐coordinated to the thiol S and heterocyclic N atoms, and the structural distortion for each is a displacement from tetragonal toward trigonal bipyramidal geometry. The complex 1 is a one‐dimensional chain complex, while compounds 3 and 4 are dimers due to the existence of N···H hydrogen bonding. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:69–75, 2005; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20068  相似文献   

4.
The organotin(IV) chlorides RnSnCl4−n (n = 3, R = Ph, PhCH2, n−Bu; and n =2, R = n−Bu, Ph, PhCH2) react with 4,4′‐bipyridine (4′4‐bpy) to give [(Ph3SnCl)2(4,4′‐bpy)1.5(C6H6)0.5] ( 1 ), [(PhCH2)3‐ SnCl]2 (4,4′‐bpy) ( 2 ), [(n−Bu)3SnCl]2(4,4′‐bpy) ( 3 ), [(n−Bu)2SnCl2(4,4′‐bpy)] ( 4 ), [Ph2SnCl2(4,4′‐bpy)] ( 5 ), and [(PhCH2)2SnCl2(4,4′‐bpy)] ( 6 ). The new complexes have been characterized by elemental analyses, IR, 1H, 13C, 119Sn NMR spectroscopy. The structures of ( 1 ), ( 2 ), ( 4 ), and ( 6 ) have been determined by X‐ray crystallography. Crystal structures of ( 1 ) and ( 2 ) show that the coordination number of tin is five. In complex ( 1 ), two different molecules exist: one is a binuclear molecule bridged by 4,4′‐bpy and another is a mononuclear one, only one N of 4,4′‐bpy coordinate to tin. Complex ( 2 ) contains an infinite 1‐D polymeric binuclear chain by weak Sn…Cl intermolecular interactions with neighboring molecules. In the complexes ( 4 ) and ( 6 ), the tin is six‐coordinate, and the 4,4′‐bpy moieties bridge adjacent dialkyltin(IV)dichloride molecules to form a linear chain. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:338–346, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20016  相似文献   

5.
The diorganotin(IV) complexes, R2Sn(dtbu) (R = Me 1 , n‐Bu 2 , Ph 3 , PhCH2 4 ; H2dtbu = 2,5‐dithiobiurea), have been synthesized and characterized by IR, 1H, and 119Sn NMR spectroscopy. The structures of 1 and 3 have been determined by X‐ray crystallography. Crystal structures show that both complexes 1 and 3 consist of molecules in which the bideprotonated ligand is N,S,S‐bonded, and the tin atom exhibits distorted pentacoordination with small differences between the methyl and phenyl derivatives in bond distances and bond angles. The unusual coordination mode of the dtbu2− anion creates four‐ and five‐membered chelate rings. Moreover, the packing of complexes 1 and 3 are stabilized by the hydrogen bonding. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:93–98, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20173  相似文献   

6.
New diorganotin(IV) complexes of a Schiff base (HL) having general formula R2Sn(L)Cl (where L is the monoanion of HL and R = n‐Bu or Ph) have been synthesized and characterized using elemental analysis, infrared, NMR (1H, 13C, 119Sn) and UV–visible spectroscopies and mass spectrometry. These investigations suggest that in these 1:1 monomeric derivatives the Schiff base ligand acts in a monoanionic bidentate manner coordinating through the Ophenolic and Nazomethine, with proposed distorted trigonal bipyramidal geometry around tin with Ophenolic and two organic groups in the equatorial plane and the Nazomethine and the third organic group in axial positions. The proposed structures have been validated by density functional theory (DFT)‐based quantum chemical calculations at the B3LYP/6‐31G(d,p)/Def2‐SVP (Sn) level of theory. The simulated UV–visible spectrum was obtained with the time‐dependent DFT method in the gas phase and in the solvent field with the integral equation formalism–polarizable continuum model. A comparative analysis of the experimental vibrational frequencies and simulated harmonic frequencies indicates a good correlation between them. An insight into the intramolecular bonding and interactions among bonds in organotin(IV) complexes of HL was obtained by means of natural bond orbital analysis. The topological and energetic properties of the electron density distribution for the tin–ligand interaction in R2Sn(L)Cl have been theoretically calculated at the bonds around the central tin atom in terms of atoms‐in‐molecules theory. The R2Sn(L)Cl complexes were screened for their in vitro antifungal activity against chosen fungal strains.  相似文献   

7.
A series of organotin(IV) complexes of two types, [R3Sn]2(dtbu) (R = PhCH2 1 , Ph 2 , n‐Bu 3 , H2dtbu = 2,5‐dithiobiurea), [R2SnCl]2(dtbu) (R = PhCH2 4 , Ph 5 , n‐Bu 6 ) have been synthesized and characterized by elemental analysis, IR, and NMR (1H, 119Sn) spectroscopy. The structures of 2 and 6 have been determined by X‐ray crystallography. Crystal structures show that both complexes 2 and 6 are the symmetric dinuclear unit. Interestingly, supramolecular structures show that complex 2 has formed a linear chain through N H⋅⋅⋅S hydrogen bonding and 6 has formed a two‐dimensional network in perfect bc plane connected through N H⋅⋅⋅Cl hydrogen bonding and nonbonded S⋅⋅⋅S interactions. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:435–442, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20456  相似文献   

8.
A series of triorganotin (4H‐1,2,4‐triazol‐4‐yl)benzoates have been synthesized by the reaction of 4‐(4H‐1,2,4‐triazol‐4‐yl)benzoic acid and 3‐(4H‐1,2,4‐triazol‐4‐yl)benzoic acid with (R3Sn)2O (R = Et, n‐Bu and Ph) or R′3SnOH (R′ = p‐tolyl and cyclohexyl). The molecular structure of tri(p‐tolyl)tin 3‐(4H‐1,2,4‐triazol‐4‐yl)benzoate determined by X‐ray crystallography displays that the tin atom adopts a five‐coordinate distorted trigonal bipyramidal geometry with the carboxyl oxygen atom and the nitrogen atom on 1‐position of triazole ring occupying the apical position. Moreover, this complex forms a polymeric chain by the intermolecular Sn–N interactions. All these complexes show good antifungal activities in vitro against Alternaria solani, Cercospora arachidicola, Gibberella zeae, Physalospora piricola, and Botrytis cinerea. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 20:411–417, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20566  相似文献   

9.
The reaction of N‐methyl‐2,2′‐diphenolamine 1 and 2,2′‐diphenolamine 2 with some diorganotin(IV) oxides [R1/2SnO: R1 = Me, n‐Bu, t‐Bu and Ph] led to the syntheses of diorgano[N‐methyl‐2,2′‐diphenolato‐O,O′,N]tin (IV) 3–6 and diorgano[2,2′‐diphenolato‐O,O′,N]tin (IV) 7–9 . All compounds (except 7 ) studied in this work were characterized by 1H, 13C, 119Sn NMR, infrared, and mass spectroscopy. Their 119Sn NMR data show that the tin atom is tetracoordinated in CDCl3 but penta and hexacoordinated in DMSO‐d6. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 133–139, 1999  相似文献   

10.
The reactions of diorganotin dichloride [Ph_2SnCl_2, (PhCH_2)_2-SnCl_2 or (n-Bu)_2SnCl_2] with potassium salt of 2,5-dimercapto-4-phenyl-1, 3, 4-thiodiazole gave complexes R_2Sn (S_3N_2C_8H_5)_2(4: R=Ph; 5: R=PhCH_2 and 6: R=n-Bu), respectively.Characterizations were carried out for all complexes by IR, ~1HNMR spectra and X-ray crystallography analysis. Including theSn…N interaction, the three complexes all have six-coordinateddistorted octahedral geometry. Based on the requence of stereo-chemical constraint sequence, phenyl≈benzyl>n-butyl, the lessthe effect of the stereochemical constraint of R groups, the  相似文献   

11.
The diorganotin(IV) complexes of methyl 2‐{4‐hydroxy‐3‐[(2‐hydroxy‐phenylimino)‐methyl]‐phenylazo}‐benzoate (H2L) were obtained by the reaction of ortho‐aminophenol, R2SnO (R = Me, nBu, or Ph) and methyl 2‐[(E)‐(3‐formyl‐4‐hydroxy)diazenyl]benzoate (H2PL2) in ethanol, which led to diorganotin(IV) compounds of composition [Me2SnL]2 ( 1 ), nBu2SnL ( 2 ), and Ph2SnL ( 3 ) in good yield. The 1H, 13C, and 119Sn NMR, IR, the mass spectrometry along with elemental analyses allowed establishing the structure of ligand (H2L) and compounds 1–3 . In all the three cases, 119Sn chemical shifts are indicators of five‐coordinated Sn atoms in a solution state. The crystal structures of ligand H2L and complexes 1 and 2 were determined by a single crystal X‐ray diffraction study. In the solid state, the ligand H2L exists as a keto‐enamine tautomeric form. The molecular structure of complex 1 in the solid state shows a distorted octahedral geometry around a tin atom due to additional coordination with an oxygen atom from a neighboring molecule leading to a four‐membered ring with Sn‐O···Sn‐O intermolecular coordination, leading to a dimeric species. On the other hand, complex 2 is a monomer with trigonal bipyramidal geometry surrounding the tin atom. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:457–465, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21037  相似文献   

12.
Four new diorganotin(IV) complexes of N‐(5‐halosalicylidene)tryptophane, R2Sn[5‐X‐2‐OC6H3CH?NCH(CH2Ind)COO] [Ind = 3‐indolyl; R, X = Et, Cl ( 1 ); Et, Br( 2 ); n‐Bu, Cl ( 3 ); n‐Bu, Br ( 4 )], were synthesized and characterized by elemental analysis, IR and NMR (1H, 13C and 119Sn) spectra. The crystal structures of complexes 1 – 3 were determined by X‐ray single crystal diffraction and showed that the tin atoms are in a distorted trigonal bipyramidal geometry and form five‐ and six‐membered chelate rings with the tridentate ligand. Intermolecular weak interactions in 1–3 link molecules, respectively, into a two‐dimensional array, a one‐dimensional infinite chain and a one‐dimensional double‐chain supramolecular structure. Bioassay results of the compounds indicated that the dibutyltin complexes 3 and 4 have potent in vitro cytotoxic activity against two human tumor cell lines, CoLo205 and Bcap37, while the diethyltin complexes 1 and 2 display weak cytotoxic activity. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

13.
Three tin(IV) complexes of 2‐benzoylpyridine N(4)‐phenylthiosemicarbazone (H2Bz4Ph) were prepared: [Sn(L)Cl3] (1), [BuSn(L)Cl2] (2) and [(Bu)2Sn(L)Cl] (3), in which L stands for the anionic ligand formed upon complexation with deprotonation and release of HCl. The complexes were characterized by a number of spectroscopic techniques. The crystal structures of H2Bz4Ph and complex 3 were determined. The antifungal activity of the ligand and its tin(IV) complexes was tested against Candida albicans. The thiosemicarbazone proved to be more active than the tin(IV) complexes. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

14.
Four new diethyltin N‐[(2‐oxyphenyl)methylene]phenylalaninates, (CH3CH2)2Sn[2‐O‐3‐X‐5‐YC6H2CH?NCH(CH2Ph)COO] (X, Y = H, H, 1 ; H, Br, 2 ; H, OCH3, 3 ; Br, Br, 4 ), have been synthesized and characterized using elemental analysis and infrared and NMR (1H, 13C and 119Sn) spectra. The crystal structures of 1 , 2 , 3 , 4 have been determined. Compounds 1 and 2 have a 12‐membered macrocyclic structure with a trimeric [Sn3O6C3] core. Each tin atom is six‐coordinated in distorted [SnC2NO3] octahedral geometry. Compound 3 is a centrosymmetric weak dimer in which the two tin centers are linked by two asymmetric Sn? O???Sn bridges involving the phenolic oxygen of the ligand and two Sn???O interactions from ether oxygen of the adjacent ligand. The coordination geometry of the tin atom can be described as a distorted pentagonal bipyramid with two ethyl groups in axial positions. Compound 4 is a novel binuclear tin complex, formed by the carboxylate of a ligand asymmetrically bridging two tin atoms, which contains a five‐coordinated tin and a six‐coordinated tin. Bioassay results have shown that the compounds have weak in vitro activity against two human tumor cell lines, A549 and CoLo205. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

15.
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.  相似文献   

16.
Reactions of di‐n‐butyltin(IV) oxide with 4′/2′‐nitrobiphenyl‐2‐carboxylic acids in 1 : 1 and 1 : 2 stoichiometry yield complexes [{(n‐C4H9)2Sn(OCOC12H8NO2?4′/2′)}2O]2 ( 1 and 2 ) and (n‐C4H9)2Sn(OCOC12H8NO2?4′/2′)2 ( 3 and 4 ) respectively. These compounds were characterized by elemental analysis, IR and NMR (1H, 13C and 119Sn) spectroscopy. The IR spectra of these compounds indicate the presence of anisobidentate carboxylate groups and non‐linear C? Sn? C bonds. From the chemical shifts δ (119Sn) and the coupling constants 1J(13C, 119Sn), the coordination number of the tin atom and the geometry of its coordination sphere have been suggested. [{(n‐C4H9)2Sn(OCOC12H8NO2?4′)}2O]2 ( 1 ) exhibits a dimeric structure containing distannoxane units with two types of tin atom with essentially identical geometry. To a first approximation, the tin atoms appear to be pentacoordinated with distorted trigonal bipyramidal geometry. However, each type of tin atom is further subjected to a sixth weaker interaction and may be described as having a capped trigonal bipyramidal structure. The diffraction study of the complex (n‐C4H9)2Sn(OCOC12H8NO2?4′)2 ( 3 ) shows a six–coordinate tin in a distorted octahedral frame containing bidentate asymmetric chelating carboxylate groups, with the n‐Bu groups trans to each other. The n‐Bu? Sn? n‐Bu angle is 152.8° and the Sn? O distances are 2.108(4) and 2.493(5) Å. The oxygen atom of the nitro group of the ligand does not participate in bonding to the tin atom in 1 and 3 . Crystals of 1 are triclinic with space group P1 and of that of 3 have orthorhombic space group Pnna. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

17.
Fourteen new diorganotin(IV) complexes of N‐(5‐halosalicylidene)‐α‐amino acid, R′2Sn(5‐X‐2‐OC6H3CH?NCHRCOO) (where X = Cl, Br; R = H, Me, i‐Pr; R′ = n‐Bu, Ph, Cy), were synthesized by the reactions of diorganotin halides with potassium salt of N‐(5‐halosalicylidene)‐α‐amino acid and characterized by elemental analysis, IR and NMR (1H, 13C and 119Sn) spectra. The crystal structures of Bu2Sn(5‐Cl‐2‐OC6H3CH?NCH(i‐Pr)COO) and Ph2Sn(5‐Br‐2‐OC6H3CH?NCH(i‐Pr)COO) were determined by X‐ray single‐crystal diffraction and showed that the tin atoms are in a distorted trigonal bipyramidal geometry and form five‐ and six‐membered chelate rings with the tridentate ligand. Bioassay results of a few compounds indicated that the compounds have strong cytotoxic activity against three human tumour cell lines, i.e. HeLa, CoLo205 and MCF‐7, and the activity decreased in the order Cy>n‐Bu>Ph for the R′ group bound to tin. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

18.
Reaction between an aqueous ethanol solution of tin(II) chloride and that of 4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl‐3 H‐pyrazol‐3‐one in the presence of O2 gave the compound cis‐dichlorobis(4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl‐3 H‐pyrazol‐3‐onato) tin(IV) [(C26H26N4O4)SnCl2]. The compound has a six‐coordinated SnIV centre in a distorted octahedral configuration with two chloro ligands in cis position. The tin atom is also at a pseudo two‐fold axis of inversion for both the ligand anions and the two cis‐chloro ligands. The orange compound crystallizes in the triclinic space group P 1 with unit cell dimensions, a = 8.741(3) Å, b = 12.325(7) Å, c = 13.922(7) Å; α = 71.59(4), β = 79.39(3), γ = 75.18(4); Z = 2 and Dx = 1.575 g cm–3. The important bond distances in the chelate ring are Sn–O [2.041 to 2.103 Å], Sn–Cl [2.347 to 2.351 Å], C–O [1.261 to 1.289 Å] and C–C [1.401 Å] the bond angles are O–Sn–O 82.6 to 87.7° and Cl–Sn–Cl 97.59°. The UV, IR, 1H NMR and 119Sn Mössbauer spectral data of the compound are reported and discussed.  相似文献   

19.
Six new triorganotin complexes ( 1a – 1c and 2a – 2c ) of 5‐(salicylideneamino)salicylic acid, [5‐(3‐X‐2‐HOC6H3CH═N)‐2‐HOC6H3COO]SnR3 (X = H, 1 ; CH3O, 2 ; R = Ph, a ; Cy, b ; CH2C(CH3)2Ph, c ), have been synthesized by one‐pot reaction of 5‐aminosalicylic acid, salicylaldehyde and triorganotin hydroxide and characterized using elemental analysis and infrared and NMR (1H, 13C and 119Sn) spectra. The crystal structures of 1a , 1b , 2a ·CH3OH, 2b ·CH3OH and 2c ·CHCl3 have been determined using single‐crystal X‐ray diffraction. In non‐coordinated solvent CDCl3, the tin atoms in the complexes are all four‐coordinated. In the crystalline state, these compounds adopt a four‐ or five‐coordination mode. Complex 1a exhibits a 44‐membered macrocyclic tetrameric structure with trigonal bipyramidal geometry around the tin atoms in which the axial positions are occupied by the oxygen atom of carboxylate group of the ligand and the phenolic oxygen atom from the adjacent ligand. The coordination geometry of tin atom in 1b and 2c ·CHCl3 is a distorted tetrahedron shaped by three carbon atoms of alkyl groups and a carboxylate oxygen atom of the ligand. In 2a ·CH3OH and 2b ·CH3OH, the tin atom has a distorted trans‐C3SnO2 trigonal bipyramidal geometry formed by three alkyl groups, a monodentate carboxylate group and a coordinated methanol molecule. The molecules of 2a ·CH3OH and 2b ·CH3OH are linked via O─H···O hydrogen bonds into a one‐dimensional supramolecular chain and a centrosymmetric R44(22) macrocycle, respectively. Bioassay results against two human tumor cell types (A549 and HeLa) show the complexes are efficient cytostatic agents and may be explored as potential antitumor drugs.  相似文献   

20.
Di‐ and triorganotin(IV) carboxylates, RnSn(OCOC(R2)=CHR1)4–n (n = 2 and 3; R = Me, Et, n‐Bu, Ph; R1 = 3‐CH3O‐4‐OHC6H3, R2 = C6H5) were prepared by reacting the corresponding organotin(IV) chloride with the silver salt of the (E)‐3‐(4‐hydroxy‐3‐methoxyphenyl)‐2‐phenylpropenoic acid. The title compounds were investigated and characterized by elemental analysis, infrared (FT‐IR), multinuclear (1H, 13C, 119Sn) NMR, and mass spectrometry, and possible structures were proposed. The complexes and ligand acid ( HL ) have been evaluated in vitro against various bacteria and fungi. The results noticed during the biocidal activity screenings proved their in vitro biological potential. They were also tested for cytotoxicity.  相似文献   

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