Biocidal Organotin Compounds. Part 2. Synthesis,Characterization and Biocidal Properties of Triorganotin(IV) Hydantoic Acid Derivatives and the Crystal Structures of Triphenyltin and Tricyclohexyltin Hydantoates

The preparation and spectroscopic (¹H NMR, UV and IR) characterization of three R₃Sn(O₂CCH₂N(H)C(O)NH₂) [R=Ph, c-Hex (cyclohexyl) or n-Bu] compounds are reported. A different mode of coordination is indicated for the hydantoate ligand in the R=Ph compound compared with the R=c-Hex and R=n-Bu compounds, as confirmed by a crystallographic analysis. The structure of [Ph₃Sn(O₂CCH₂N(H)C(O)NH₂)] is polymeric owing to the presence of bridging hydantoate ligands such that each ligand coordinates one tin atom, via one of the carboxylate oxygen atoms, and a symmetry-related tin atom via the carbonyl group at the other end of the molecule. The structure features distorted trigonal-bipyramidal tin atom geometries with a trans -R₃SnO₂ motif. The structure of [c-Hex₃Sn(O₂CCH₂N(H)- C(O)NH₂)], by contrast, is monomeric, distorted tetrahedral, as the carboxylate group is monodentate and there are no additional tin–ligand interactions. The structures are each stabilized by a number of intermolecular hydrogen bonds. Fungitoxicity and phytotoxicity studies indicate that the R=n-Bu derivative is the more active compound.     

Structural Characterization of (Arylimido)vanadium(V) Compounds with 2,6‐Difluorophenoxide Ligand

The (arylimido)vanadium(V) compound, [(p‐MeOC₆H₄N)V(OiPr)₃] was demonstrated to undergo ligand exchange reaction with one or two equivalents of 2,6‐difluorophenol, affording the (arylimido)vanadium(V) compounds, [(p‐MeOC₆H₄N)V(OiPr)₂(O‐2,6‐F₂Ph)] and [(p‐MeOC₆H₄N)V(OiPr)(O‐2,6‐F₂Ph)₂]. Their X‐ray crystallographic analyses elucidated the μ‐isopropoxido‐bridged dimeric structures, wherein each vanadium atom has a trigonal‐bipyramidal arrangement with the imido and bridging isopropoxide ligands in the apical positions. The isopropoxide ligand was selectively employed as a bridging ligand between two central vanadium atoms. On the other hand, the reaction of the (arylimido)vanadium(V) compound, [(p‐MeOC₆H₄N)VCl₃] and three equivalents of lithium 2,6‐difluorophenoxide gave the (arylimido)vanadium(V) compound, [(p‐MeOC₆H₄N)V(O‐2,6‐F₂Ph)₃]. In the crystal packing, the thus‐obtained compound showed a distorted trigonal‐bipyramidal environment at the vanadium atoms with the μ‐phenoxido‐bridged dimeric structure, wherein the 2,6‐difluorophenoxide ligand was found to serve as a bridging ligand.     

Correlation between quadrupole splitting (Δ) and the θ angle (C–Sn–C) in five-coordinate diphenyltin(IV) complexes. X-ray crystal structures of [Ph2Sn(hacm)] and [Ph2Sn(hacmm)] containing O , N , S -tridentate N 4-heterocyclic thiosemicarbazones

2-Hydroxyacetophenone N ⁴-morpholylthiosemicarbazone (H₂hacm) and 2-hydroxyacetophenone N ⁴-2,6-dimethylmorpholylthiosemicarbazone (H₂hacmm) form stable five-coordinate complexes of the compositions [Ph₂(hacm)] and [Ph₂Sn(hacmm)], respectively, which were characterized by elemental analysis and spectroscopic (i.r., n.m.r. and M?ssbauer) studies. Both complexes and the H₂hacm ligand were also studied by single crystal X-ray diffraction. The X-ray structures determination of complexes revealed the presence of neutral molecules in which the tin(IV) atoms exhibit distorted trigonal bipyramidal (TBP) geometry, with the O,N,S-tridentate bifunctional behavior of the ligand. The C–Sn–C angles were calculated using a correlation between M?ssbauer and X-ray data based on the point-charge model.     

A 1:1 adduct between di­methyl­tin dibromide and N‐methyl­pyrrolidinone (NMP)

The title compound, di­bromo­di­methyl(N‐methyl­pyrrolidin‐2‐one‐O)­tin(IV), [SnBr₂(CH₃)₂(C₅H₉NO)], exhibits pentacoordination of the Sn atom, with long and short Sn—Br bonds [2.6737 (4) and 2.5256 (4) Å, respectively]. The distorted trigonal–bipyramidal coordination polyhedron has two methyl groups and one Br atom in the equatorial plane, the second Br atom and the N‐methyl­pyrrolidinone (NMP) ligand occupying the apical positions.     

Diorganotin(IV) and triorganotin(IV) derivatives of diphenic acid

The diorganotin(IV) and triorganotin(IV) derivatives R₂SnA (R = Me, n-Pr, n-Bu, n-Oct) and (R₃Sn)₂A [R = Me, Ph, cyclohexyl (Cyh); A = an anion of diphenic acid] have been prepared and characterized by elemental analysis, IR, ¹H and ¹³C NMR spectroscopies. Tetrahedral tin forms a part of a diphenate cyclic ring in the diorganotin complexes with unidentate carboxylates, which have further been used for the synthesis of cyclic acid anhydrides. The soluble dinuclear triorganotin complexes (Me, Ph) possess symmetrically bonded carboxylates while the less soluble compound (Cyh₃Sn)₂A has two asymmetrically bonded carboxylates. All have a trigonal bipyramidal structure with R₃Sn units remote from each other.     

(N‐Maleoylglycinato)trimethyltin(IV)

The Sn atom in the crystal structure of the title compound,catena‐poly­[trimethyl­tin‐μ‐[(2,5‐di­oxo‐2,5‐di­hydro­pyrrol‐1‐yl)­acetato‐O:O′]], [Sn(CH₃)₃(C₆H₄NO₄)], adopts a distorted trigonal bipyramidal coordination geometry with three methyl groups defining the trigonal plane [mean Sn—C 2.117 (11) Å] and the axial positions occupied by O atoms from different carboxylate groups, with significantly different Sn—O bond lengths [2.207 (5) and 2.358 (6) Å]. The structure forms a polymeric chain of complex molecules linked via carboxylate moieties.     

Structural chemistry of organotin carboxylates: I. The crystal structure of di-n-butylbis(thiophenoxyacetato)tin(IV): nBu2Sn(O2CCH2SC6H5)2

A crystal structure study of ⁿBu₂Sn(O₂CCH₂SC₆H₅)₂ reveals the compound to be monomeric with the tin atom situated on a crystallographic 2-fold axis in a skew-trapezoidal bipyramidal geometry. The basal plane is defined by two asymmetrically chelating carboxylate groups; SnO 2.134(4) and 2.559(5) Å and the ⁿBuSnⁿBu angle is 140.7(2)°. The sulphur atoms do not participate in any significant interactions to the tin atom. Crystals are monoclinic with space group C2 and unit cell dimensions a 18.668(6), b 15.761(6), c 5.106(5) Å, β 117.55(5)°; Z = 2. The structure was refined by a full-matrix least-squares procedure to final R = 0.034 and R_w = 0.033 for 1294 reflections with I ≥ 2.5σ(I).     

Crystallographic report: Bis[tri(o‐chlorobenzyl)tin(IV)] terephthalate

The centrosymmetric structure of (o‐ClC₆H₄)₃SnO₂CC₆H₄CO₂Sn(C₆H₄Cl‐o)₃ features an unsymmetrically chelating carboxylate group, so that a distorted trigonal bipyramidal cis‐C₃O₂ coordination geometry for tin results. Copyright © 2004 John Wiley & Sons, Ltd.     

Chloro­di­methyl(N‐methyl­pyrrolidin­one)­tin(IV)‐μ‐chloro‐di­chloro­di­methyl­tin(IV)

The synthesis and the X‐ray structural analysis of the title compound, μ‐chloro‐1:2κ²Cl‐tri­chloro‐1κCl,2κ²Cl‐tetra­methyl‐1κ²C,2κ²C‐(N‐methyl­pyrrolidin‐2‐one)‐1κO‐ditin(IV), [Sn₂Cl₄(CH₃)₄(C₅H₉NO)], are described. The title compound is found to exhibit a distorted trigonal–bipyramidal geometry at both Sn^IV atoms. The Sn—Cl—Sn angle involving the bridging chlorine ligand is 135.56 (5)°, with the Sn—Cl bond lengths being 2.5704 (13) and 3.1159 (13) Å.     

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.     

丙酮酸异烟酰腙四核有机锡配合物的合成、表征及{[nBu2Sn(C9H8N3O3)O]SnBu3n}2的晶体结构

The tetranuclear alkyltin(Ⅳ) compounds {[R2Sn(C9H8N3O3)O]SnR3}2 [R=n-Bu (1), 4-CNC6H4CH2 (2),C6H5CH2 (3), 4-ClC6H4CH2 (4)] were prepared by the reaction of Schiff base ligand pyruvic acid isonicotinyl hydrazone with (R3Sn)2O in the corresponding molar ratio of 1:1. All compounds have been characterized by elemental analysis, IR and ^1H NMR spectra. The crystal structure of compound 1 was determined by X-ray single crystal diffractional analysis. This compound exhibits a dimeric structure containing distannoxane units with two types of the tin atoms. For the first tin atom, it appears to be seven-coordinated with a distorted pentagonal bipyramid geometry, and the other is five-coordinated with a distorted trigonal bipyramidal geometry. The molecules are packed in the unit cell in two-dimensional network structure through an interaction between the N atoms of the pyridine and the tin atoms of an adjacent molecule.     

Synthesis and characterization of di‐n‐butyltin(IV) complexes with 4′/2′‐nitrobiphenyl‐2‐carboxylic acids: X‐ray crystal structures of [{(n‐C4H9)2Sn(OCOC12H8NO2−4′)}2O]2 and (n‐C4H9)2Sn{OCOC12H8NO2−4′}2

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.     

Crystallographic report: The two‐dimensional crystal structure of bis(trimethyltin)succinate, [(Me3Sn)2(O2CCH2CH2CO2)]∞

A two‐dimensional layer structure is found in the title compound comprising interconnected 22‐membered rings and trans‐C₃O₂ trigonal bipyramidal coordination geometries for tin. Copyright © 2003 John Wiley & Sons, Ltd.     

Molecular structures of [(Ph3Sn)2O3Se] and [(Ph3Sn)2O4Cr](CH3OH)

Molecular structures of [(Ph₃Sn)₂O₃Se] (1) and [(Ph₃Sn)₂O₄Cr](CH₃OH) (2) have been determined using spectroscopic techniques and X-ray analysis. Each structure consists of polymers containing two types of tin centres: one of them is bridged by two oxygen atoms of the trifunctional oxyanion into a helical chain while the other is pendant to this chain. In the case of the chromato derivative the pendant tin is also bonded to the oxygen atom of the solvent (methanol); hydrogen bonds between the methanol and the non-coordinated oxygen of the chromate generate a three-dimensional structure containing tin atoms in a trigonal bipyramidal environment. In contrast, the two tin centres in the non-solvated selenito derivative have distinct geometries (tetrahedral and trigonal bipyramidal). Variable temperature Mössbauer spectroscopy data are consistent with the polymeric structure of the selenito derivative while NMR spectroscopy shows the presence of monomeric species in solution.     

[N-(4-Chloro­benzoyl)-N′-(picolinyl­idene)hydrazinato]dioxovanadium(V)

In the structure of the title compound (systematic name: {(4-chlorophenyl)[2-(2-pyridyl­methyl­idene-κN)­hy­dra­zono-κN²]methanolato-κO}­di­oxo­vana­dium(V)), [VO₂(C₁₃H₉ClN₃O)], the asymmetric unit contains three independent but geometrically similar mol­ecules. The metal centre has a distorted trigonal bipyramidal N₂O₃ coordination sphere. The planar monoanionic N,N,O-donor ligand occupies one equatorial and two axial positions, the remaining two equatorial positions being occupied by the two oxo groups.     

Crystal structures of two polymeric bis(triphenyltin) malonates

In an attempt to prepare potassium/sodium salts of malonato-triphenylstannate, two bis(triphenyltin) malonates were obtained instead, [(C₆H₅)₃Sn]₃[O₂CCH₂CO₂]_1.5 (1) and {[(C₆H₅)₃SnO₂CCH₂CO₂Sn(C₆H₅)₃]H₂O}CH₃CH₂OH (2). This provides an excellent example of structural diversity in triorganotin carboxylates. In both complexes, the dicarboxylate was connected to the triphenyltin groups forming a linear infinite polymeric chain. Both complexes have a trans-trigonal bipyramidal geometry with the three phenyl groups occupying the equatorial plane and two oxygens at axial positions. Both short and long tin–oxygen distances were observed in 1 and 2. In 1, all carboxylates functioned as bridging bidentate ligands, resulting in an infinite 3-D polymer network propagating along all three axes. In 2, Sn1 is bonded to a carboxylate and a water molecule (Sn1–O1 2.145(3)?Å, Sn1–O3 2.341(3)?Å, O1–Sn1–O3 173.97(12)°). Only one carboxylate acts as a bidentate ligand allowing the carbonyl group to be axially coordinated to the adjacent tin, Sn2. Also, Sn2 is covalently bonded to the other carboxylate group in the malonate ligand (Sn2–O4 2.163(3)?Å, Sn2–O5 2.353(3)?Å, O4–Sn2–O5 173.47(12)°). There is a water molecule included in the crystal lattice hydrogen bonded to the uncoordinated carbonyl in malonate.     

Tetra­butyl­bis(N‐phthaloyl­glycinato)­distannoxane dimer

The crystal structure of the title compound, [Sn₄(C₄H₉)₈(C₁₀H₆NO₄)₄O₂], contains centrosymmetric dimers. It contains a central Sn₂O₂ core with the O atoms bonded to two di­butyl­bis(N‐phthaloyl­glycinato)­tin units. The Sn atoms of the core are six‐coordinate in a skew trapezoidal bipyramidal geometry, while the exocyclic Sn atoms are essentially five‐coordinate in a distorted trigonal geometry. The Sn—C distances lie in a narrow range of 2.120 (5)–2.138 (4) Å.     

Tin(IV) and organotin(IV) derivatives of novel β-diketones: Part IV. Triorganotin(IV) complexes of fluorinated 4-acyl-5-pyrazolones. Crystal structure of (1-(4-trifluoromethylphenyl)-3-methyl-4-acetylpyrazolon-5-ato)triphenyltin(IV)

The synthesis of three 1-(4-trifluoromethylphenyl)-3-methyl-4-R¹(C=O)-5-pyrazolone proligands LH (L¹H; R¹=C₆H₅: L²H; R¹=CH₃: L³H; R¹=CF₃) and their interaction with R₃Sn(IV) acceptors (R=Me, Buⁿ, Ph) are reported. When R=Me or Buⁿ, aquo (4-acylpyrazolonate)SnR₃(H₂O) derivatives are obtained and the anionic donors 4-acylpyrazolonate (L⁻) act in the O–monodentate form. These triorganotin complexes are not stable in chlorohydrocarbon solvents and decompose to R₄Sn and bis(4-acyl-5-pyrazolonate)₂SnR₂. When R=Ph, stable (4-acyl-5-pyrazolonate)SnPh₃ derivatives, both in solution and in the solid state, are obtained. The crystal structure of (1-(4-trifluoromethylphenyl)-3-methyl-4-acetylpyrazolon-5-ato)triphenyltin(IV) shows a five-coordinate tin atom in a strongly distorted cis-bipyramidal trigonal environment (axial angle=161.2(2)°) with the acylpyrazolonate donor acting as an asymmetric O₂–bidentate species (Sn–O(1)=2.081(6) Å: Sn–O(2)=2.424(5) Å). Electronic effects are responsible for the different behavior shown by these trialkyl and triphenyl derivatives.     

Synthesis,structural characterization and cytotoxic activity of diorganotin(IV) complexes of N‐(5‐halosalicylidene)‐α‐amino acid

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.     

Design,synthesis and theoretical analysis of functionalized dicarboxylate moieties based on organotin(IV) dinuclear complexes: crystal structure elucidation and biological studies

Dinuclear tin(IV) dicarboxylate complexes of the types [(n-Bu)₂Sn(oda)(4-pic)]₂·2H₂O (1) and [(n-Bu)₂Sn(pda)(H₂O)]₂ (2) [H₂oda = oxydiacetic acid; H₂pda = pyridine 2,6-dicarboxylic acid) were synthesized and characterized via physicochemical and spectroscopic studies. The spectroscopic results indicated that Sn is seven-coordinate having pentagonal bipyramidal (pbp) geometry in both complexes. The X-ray study of complex 2 further specified pentagonal bipyramidal geometry with dinuclear structural arrangement due to the involvement of carboxylate bridges formed by pda^2? moiety. The crystal structure is further stabilized by different weak interactions viz., C–C?H, C–C?O, C–H?O, C–C?O, and C–H?H. These interactions are further supported by Hirshfeld surface analysis along with 2-D fingerprint plots of complex 2. In vitro DNA-binding studies of both complexes were evaluated using spectroscopic techniques (absorbance and fluorescence) which ascertained optimum binding affinity of both complexes. However, cleavage activity of the complexes was assessed using supercoiled DNA (pBR322) via gel electrophoresis technique which demonstrated significant cleavage pattern of both complexes at different concentrations. Furthermore, chemotherapeutic potential of complexes 1 and 2 against MCF-7 and Hep carcinoma cell lines also suggested significant antiproliferative effect of complexes. These results revealed momentous exploration of drug–DNA interactions which may engender new insinuation for the advancement of metallo-pharmaceuticals.