Synthesis and characterization of bis[dicarboxylatotetraorganodistannoxane] units involving 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acids: an investigation of structures by X-ray diffraction, NMR, electrospray ionisation MS and assessment of in vitro cytotoxicity.
Abstract Reactions of 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acids (LHH′, where the aryl group is an R-substituted phenyl ring such that for L1HH′: R = H; L2HH′: R = 2′-CH3; L3HH′: R = 3′-CH3; L4HH′: R = 4′-CH3; L5HH′: R = 4′-Cl; L6HH′: R = 4′-Br) with nBu2SnO in a 1:1 molar ratio yielded complexes of composition {[nBu2Sn(LH)]2O}2. The complexes have been characterized by 1H, 13C, 119Sn NMR, ESI-MS, IR and 119mSn Mossbauer spectroscopic techniques in combination with elemental analyses. The crystal structures of {[nBu2Sn(L1H)]2O}2 (1), {[nBu2Sn(L4H)]2O}2 (4), {[nBu2Sn(L5H)]2O}2 (5) and {[nBu2Sn(L6H)]2O}2 (6) were determined. The compounds are centrosymmetric tetranuclear bis(dicarboxy…
Crystal and solution structures of di-n-butyltin(IV) complexes of 5-[(E)-2-(4-methoxyphenyl)-1-diazenyl]quinolin-8-ol and benzoic acid derivatives: En route to elegant self-assembly via modulation of the tin coordination geometry
Abstract Reactions of nBu2SnCl(L1) (1), where L1 = acid residue of 5-[(E)-2-(4-methoxyphenyl)-1-diazenyl]quinolin-8-ol, with various substituted benzoic acids in refluxing toluene, in the presence of triethylamine, yielded dimeric mixed ligand di-n-butyltin(IV) complexes of composition [nBu2Sn(L1)(L2–6)]2 where L2 = benzene carboxylate (2), L3 = 2-[(E)-2-(2-hydroxy-5-methylphenyl)-1-diazenyl]benzoate (3), L4 = 5-[(E)-2-(4-methylphenyl)-1-diazenyl]-2-hydroxybenzoate (4), L5 = 2-{(E)-4-hydroxy-3-[(E)-4-chlorophenyliminomethyl]-phenyldiazenyl}benzoate (5) and L6 = 2-[(E)-(3-formyl-4-hydroxyphenyl)-diazenyl]benzoate (6). All complexes (1–6) have been characterized by elemental analyses, IR, 1H,…
Self-assembly of extended Schiff base amino acetate skeletons, 2-{[(2Z)-(3-hydroxy-1-methyl-2-butenylidene)]amino}phenylpropionate and 2-{[(E)-1-(2-hydroxyaryl)alkylidene]amino}phenylpropionate skeletons incorporating organotin(IV) moieties: Synthesis, spectroscopic characterization, crystal structures, and in vitro cytotoxic activity
The organotin(IV) compounds, [Ph 3 SnL 1 H] n · nCCl 4 ( 1 ), [Me 2 SnL 2 (OH 2 )] ( 2 ), [ n Bu 2 SnL 2 ] ( 3 ), [Ph 2 SnL 2 ] n ( 4 ), [Ph 3 SnL 2 H] n ( 5 ) and [Ph 3 SnL 3 H] n ( 7 ) (L 1 = 2-{[(2 Z )-(3-hydroxy-1-methyl-2-butenylidene)]amino}phenylpropionate and L 2−3 = 2-{[( E )-1-(2-hydroxyaryl)alkylidene]amino}phenylpropionate), were synthesized by treating the appropriate organotin(IV) chloride(s) with the potassium salt of the ligand in a suitable solvent, while [ n Bu 2 SnL 3 (OH 2 )] ( 6 ) was obtained by reacting the acid form of L 3 (generated in situ) with n Bu 2 SnO. These complexes have been characterized by 1 H, 13 C, 119 Sn NMR, ESI-MS, IR and 119m Sn Mossbauer spectro…
Synthesis and characterization of the first diorganotin(IV) complexes containing mixed arylazobenzoic acids and having skew trapezoidal bipyramidal geometry
Abstract Three diorganotin(IV) complexes of the type, [R 2 Sn(L a H)(L b H)] (R = n Bu or Me and, L a H and L b H are two different 5-[( E )-2-(aryl)-1-diazenyl]-2-hydroxybenzoate residues; a: aryl = 4′-Cl-(held constant) and b: aryl = 4′-Me or 4′-Br) have been prepared either by reacting n Bu 2 SnO, L a HH′ and L b HH′ (1:1:1) in anhydrous toluene or by reacting Me 2 SnCl 2 , L a HNa and L b HNa (1:1:1) in anhydrous methanol. The products were characterized by microanalysis, IR, NMR ( 1 H, 13 C, 119 Sn) and 119m Sn Mossbauer spectroscopy. A full characterization of the structures of the complexes [ n Bu 2 Sn(L a H)(L b H)] ( 1 and 2 ) and [Me 2 Sn(L a H)(L b H)] ( 3 ) in the solid state w…
A polymeric two-dimensional mixed-metal network. Crystal structure and magnetic properties of {[P(Ph)4][MnCr(ox)3]}
Abstract The mixed-metal ferromagnet {[P(Ph) 4 ][MnCr(ox) 3 ]} n , where Ph is phenyl and ox is oxalate, has been prepared and a two-dimensional network structure, extended by Mn(II)-ox-Cr(III) bridges, has been determined from single crystal X-ray data. Crystal data: space group R 3 c , a = b =18.783(3), c =57.283(24) A, α=β=90, γ=120°, Z =24 (C 30 H 20 O 12 PCrMn). The magnetic susceptibility data obey the Curie-Weiss law in the temperature range 260–20 K with a positive Weiss constant of 10.5 K. The temperature dependence of the molar magnetization exhibits a magnetic phase transition at T c =5.9 K. The structure is discussed in relation to the strategy for preparing molecular based ferr…
Synthesis and Structures of Two Triorganotin(IV) Polymers R3Sn{O2CC6H4[N=C(H)}{C(CH3)CH(CH3)-3-OH]-p} n (R = Me and Ph) Containing a 4-[(2Z)-(3-Hydroxy-1-methyl-2-butenylidene)amino] benzoic Acid Framework
Two new polymeric triorganotin(IV) complexes R3Sn{O2CC6H4[N=C(H)}{C(CH3)CH(CH3)-3-OH]-p} n ([Me3Sn(LH)] n : 1) and ([Ph3Sn(LH)] n : 2) containing a 4-[(2Z)-(3-hydroxy-1-methyl-2-butenylidene)amino]benzoate (LH) framework were prepared. Both compounds have been characterized by 1H, 13C, 119Sn NMR, IR and 119Sn Mossbauer spectroscopic techniques in combination with elemental analyses. The crystal structures of complexes 1 and 2 reveal that they exist as polymeric zig-zag chains in which the LH-bridged Sn-atoms adopt a trans-R3SnO2 trigonal bipyramidal configuration with R groups in the equatorial positions and the axial sites occupied by an oxygen atom from the carboxylate ligand and the alco…
Di-n-octyltin(IV) complexes with 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acid: Syntheses and assessment of solid state structures by 119Sn Mössbauer and X-ray diffraction and further insight into the solution structures using electrospray ionization MS, 119Sn NMR and variable temperature NMR spectroscopy
Abstract Reactions of 5-[( E )-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acids (LHH′, where the aryl group is an R-substituted phenyl ring such that for L 1 HH′: X = H; L 2 HH′: X=2′-OCH 3 ; L 3 HH′: X = 3′-CH 3 ; L 4 HH′: X = 4′-CH 3 ; L 5 HH′:X = 4′-Cl) with n Oct 2 SnO in 2:1 and 1:1 molar ratios have been investigated. Two types of complexes, n Oct 2 Sn(LH) 2 and {[ n Oct 2 Sn(LH)] 2 O} 2 , were isolated and they have been characterized by 1 H, 13 C, 119 Sn NMR, ESI-MS, IR and 119m Sn Mossbauer spectroscopic techniques in combination with elemental analyses. The crystal structures of n Oct 2 Sn(L 1 H) 2 ( 1 ), {[ n Oct 2 Sn(L 2 H)] 2 O} 2 ( 3 ) and {[ n Oct 2 Sn(L 3 H)] 2 O} 2 ( 4 ) were de…
Synthesis and characterization of triphenyltin(IV) 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoates. Crystal and molecular structures of Ph3Sn{O2CC6H3-p-OH[NN(C6H4-4-CH3)]} and the 2,2′-bipyridine adduct Ph3Sn{O2CC6H3-p-OH[NN(C6H4-2-CH3)]}OH2·C10H8N2
Abstract Triphenyltin 5-[(E)-2-(4-methylphenyl)-1-diazenyl]-2-hydroxybenzoate, Ph3SnL2H, has been prepared and characterized, its structure determined by X-ray crystallography, and the structure compared with those of its homologues. Two polymorphs were isolated from the same crystallization attempt. The reactivity of tetrahedral Ph3SnL1H (L1H = 5-[(E)-2-(2-methylphenyl)-1-diazenyl]-2-hydroxybenzoate) towards 2,2′-bipyridine (bipy) has been investigated to ascertain the ability of bipy to coordinate to the Sn-complex and the resultant changes in the molecular architecture. The crystal structure of the product revealed that the bipy moiety does not coordinate to the Sn atom, but forms a cycl…
Synthesis, characterization and crystal structures of polymeric and dimeric triphenyltin(IV) complexes of 4-[((E)-1-{2-hydroxy-5-[(E)-2-(2-carboxyphenyl)-1-diazenyl]phenyl}methylidene)amino]aryls
Abstract The triphenyltin(IV) complexes of 4-[((E)-1-{2-hydroxy-5-[(E)-2-(2-carboxyphenyl)-1-diazenyl]phenyl}methylidene)amino]aryls (aryls = 4-CH3, 4-Br, 4-Cl, 4-OCH3) have been synthesized and characterized by 1H-, 13C-, 119Sn-NMR, ESI mass spectrometry, IR and 119mSn Mossbauer spectroscopic techniques in combination with elemental analysis. The crystal structures of a representative carboxylate ligand (aryl = 4-CH3) and three Sn complexes, viz., polymeric (Ph3Sn[O2CC6H4{N N(C6H3-4-OH(C(H) NC6H4X-4))}-o])n (X = Me (1) and Br (2)) and dimeric (Ph3Sn[O2CC6H4{N N(C6H3-4-OH(C(H) NC6H4X-4))}-o])2 (X = OMe (4)) complexes are reported. The coordination environment in each complex is trigonal bip…
Synthesis, characterization, cytotoxic activity and crystal structures of tri- and di-organotin(IV) complexes constructed from the β-{[(E)-1-(2-hydroxyaryl)alkylidene]amino}propionate and β-{[(2Z)-(3-hydroxy-1-methyl-2-butenylidene)]amino}propionate skeletons
Abstract Reactions of potassium β-{[(E)-1-(2-hydroxyaryl)alkylidene]amino}propionates (L1HK-L3HK) and potassium β-{[(2Z)-(3-hydroxy-1-methyl-2- butenylidene)]amino}propionate (L4HK) with R3SnCl (R = Ph and nBu) and nBu2SnCl2 yielded complexes of composition Ph3SnL1H (1), Ph3SnL2H (2), Ph3SnL4H (3), nBu3SnL1H (4), and {[nBu2Sn(L2H)]2O}2 (5) and {[nBu2Sn(L3H)]2O}2 (6), respectively. These complexes have been characterized by 1H, 13C, 119Sn NMR, ESI-MS, IR and 119mSn Mossbauer spectroscopic techniques in combination with elemental analyses. The crystal structures of 1, 4, 5 and 6 were determined. In the solid state, compound 1 is a one-dimensional polymer built from SnPh3 moieties bridged by s…