Rufen Zhang

Synthesis and structure of a novel trinuclear 18-membered macrocycle of diphenyltin complexes with 2-mercaptonicotinic acid

Abstract The 18-membered stereoregular diphenyltin macrocycles: {Ph2Sn[S(C6H3NO)O]}3 (8), {Ph2Sn[S(C6H3NO)O]}3·2.67H2O (9) and {Ph2Sn[S(C6H3NO)O]}3·4C6H6 (10) have been synthesized by the reaction of diphenyltin dichloride with 2-mercaptonicotinic acid. The three complexes were characterized by elemental, IR, 1H-NMR analyses. The X-ray crystallography analyses of 9 and 10 were also given. Single crystal X-ray diffraction data reveal that both 9 and 10 are highly symmetrical tri-nuclear cyclic complexes with the ligand 2-mercaptonicotinic acid bridging the adjacent tin atoms. The tin environment is distorted cis-trigonal bipyramid. Weak interaction Sn⋯O was recognized between tin and exocyclic-oxygen atoms. The potential tridentate of endocyclic sulfur atoms make them interesting ligands.

Self-assembly and characterization of a novel 2D network polymer containing a 60-membered organotin macrocycle.

The reaction of 1-(4-carboxyphenyl)-5-mercapto-1 H-tetrazole with trimethyltin chloride in the presence of sodium ethoxide in benzene affords a novel 2D organotin network structure complex 1, which is an unusual organotin network containing a hexanuclear 60-membered organotin macrocycle. The complex has been characterized by elemental analysis, IR, and (1)H, (13)C, and (119)Sn NMR spectroscopy. Furthermore, we have also characterized the complex by X-ray crystallography.

Syntheses, characterizations, crystal structures, and in vitro antitumor activities of chiral triorganotin(IV) complexes containing (S)-(+)-2-(4-isobutyl-phenyl)propionic and (R)-(+)-2-(4-hydroxyphenoxy)propionic acid ligands

Four new chiral triorganotin(IV) carboxylates, [(R3Sn)(O2C13H17)] n (R = Me 1, Ph 2), [(R3Sn)(O2C13H17)] (R = n-Bu 3), and [(R3Sn)(O4C9H9)] n (R = Me 4), have been synthesized by reaction of (S)-(+)-2-(4-isobutyl-phenyl)propionic acid and (R)-(+)-2-(4hydroxyphenoxy)propionic acid with triorganotin(IV) chloride in the presence of sodium ethoxide. The complexes have been characterized by elemental analyses, FT-IR, NMR (1H, 13C, and 119Sn) spectra, and X-ray crystallography diffraction analyses. Structural analyses show that 1 has a 1-D infinite chiral zigzag chain structure. Complexes 2 and 4 have a 1-D spring-like chiral helical chain with a channel, while 3 is a monomer. Antitumor activities of 1–4 have been studied.

Triorganotin(IV) complexes with substituted benzeneseleninic acids: syntheses, characterization, crystal structures, and antitumor activity

Nine new organotin(IV) selenites have been prepared by the reaction of 2-methylbenzeneseleninic acid, 2-methoxybenzeneseleninic acid, 4-isopropylbenzeneseleninic acid, and the corresponding triorganotin(IV) chloride with sodium ethoxide in methanol. The complexes have been characterized by elemental analysis, FT-IR, (1H, 13C, and 119Sn) NMR spectroscopy, and thermogravimetric analysis. Except for 3, 6, and 9, all of the complexes were also characterized by X-ray crystallography diffraction analyses. The structural analyses reveal that 1, 2, 4, 5, 7, and 8 exhibit 1-D infinite chain structures which are generated by bidentate oxygen atoms and five-coordinated tin. Complex 5 forms a 2-D organotin framework linked by intermolecular C–H ··· O interactions. Additionally, 1 and 2 were tested for antitumor activity in vitro.

Novel μ2-oxo-bridged dinuclear aryltelluronic triorganotin(IV) esters: syntheses, structural characterizations, and in vitro cytotoxicity

Four new μ2-oxo-bridged dinuclear aryltelluronic triorganotin esters [ArTe(μ-O)(OH)(OSnR3)2]2 (Ar = n-propyl-Ph, R = Me: 1, R = Ph: 2; Ar = i-propyl-Ph, R = Me: 3, R = Ph: 4) were synthesized by reaction of μ2-oxo-bridged dinuclear aryltelluronic acids and the corresponding R3SnCl (R = Me, Ph) with potassium hydroxide in methanol. The complexes were characterized by X-ray crystallography, elemental analysis, FT-IR, and NMR (1H, 13C, 119Sn) spectroscopy. The structural analysis indicates that these complexes are isostructural and crystallized as Sn4Te2 molecules, in which the asymmetric four-membered Te2(μ2-O)2 units are situated in the center. The geometry of tellurium is described as a distorted octahedron and each tin is described as a distorted tetrahedron. Complex 2 has a 2-D network structure connected by intermolecular C–H⋯π interactions. Complexes 1–4 were tested for in vitro cytotoxicity against human lung cancer cells (A549) and human hepatocellular carcinoma cells (HepG2). Graphical Abstract

Syntheses and crystal structures of polymeric ionic triorganotin esters of 3,5-pyridinedicarboxylic acid and 5-nitroisophthalic acid

The triethylammonium dicarboxylatotriorganostannates, [(C2H5)3NH][R3Sn(3,5-pdc)] · mH2O (3,5-pdc = 3,5-pyridinedicarboxylate) (m = 1, R = Me 1; m = 0, R = Ph 2, PhCH2 3, n-Bu 4), [(C2H5)3NH][R3Sn(5-nip)] (5-nip = 5-nitroisophthalate) (R = Me 5, Ph 6, PhCH2 7, n-Bu 8) have been prepared from triethylamine, 3,5-pyridinedicarboxylic acid, 5-nitroisophthalic acid and triorganotin chloride. Complexes 1–8 have been characterized by elemental, IR, 1H, 13C and 119Sn NMR analyses. Complexes 1, 2, 5 and 6 are also determined by single crystal X-ray diffraction. For 1, 2, 5 and 6, each carboxylate moiety is involved in coordination to a tin center via only one O atom showing that the Sn atoms are five-coordinate and exist in trigonal bipyramidal geometries. Moreover, for 2, 5 and 6, the nitrogen atoms of ammonium are hydrogen bonded to the pendant carboxyl oxygen. In 1, adjacent polymeric chains and triethylammonium are linked by hydrogen bonds through the co-crystallized water molecule, thus a 2D network is formed.

Novel organotin complexes derived from 2,2′-selenodiacetic acid: synthesis and biological evaluation

The reactions of 2,2′-selenodiacetic acid and the corresponding organotin(IV) chloride with sodium ethoxide in ethanol, or via a solvothermal synthetic route, have afforded four organotin polymers, namely, [(Me3Sn)2Se(CH2COO)2]n (1), [(Me2Sn)2Se(CH2COO)2(μ3-O)]n (2), [(Bu3Sn)2Se(CH2COO)2]n (3), and [(Bu2Sn)Se(CH2COO)2]n (4). All the complexes were fully characterized by elemental analysis, FT-IR, NMR (1H, 13C, and 119Sn) spectroscopy and single crystal X-ray diffraction analysis. The structural analysis reveals that complex 1 is a 2D-polymer containing interconnected 24-membered (Sn4O8C10Se2) macrocyclic rings. Unlike complex 1, the 2D polymer structure of complex 2 is made up of the typical ladder tetraorganodistannoxane unit containing 32-membered (Sn4O8C16Se4) macrocyclic rings. Complex 3 is a 3D corrugated polymeric structure in which the deprotonated dicarboxylic acid acts as a tetradentate ligand by four oxygen atoms. Complex 4 is a 1D zigzag coordination polymer and the tin coordination geometry is described as skewed-trapezoidal bipyramidal. In particular, preliminary cytotoxic assessments of the involvement of complex 4 in the apoptotic death of MDA cells were conducted, and the results revealed that the antiproliferative and proapoptotic effect of complex 4 in MDA cells prominently contributed to the overload of intracellular ROS levels and the dysfunctional depolarization of mitochondrial membranes.

Syntheses and structural characterization of organotin complexes derived from 2-(trifluoromethyl)benzeneseleninic acid: tetranuclear macrocycle, 1-D polymeric chain, helical double-chain

Abstract Four organotin(IV) complexes based on 2-(trifluoromethyl)benzeneseleninic acid, [Me3Sn(O2SeC6H4-2-CF3)]4 (1), [Ph3Sn(O2SeC6H4-2-CF3)]n (2), [R2Sn(O2SeC6H4-2-CF3)2]n (R = Me 3; n-Bu 4), have been synthesized and characterized by X-ray diffraction, elemental analysis, infrared spectroscopy, and NMR (1H, 13C and 119Sn) spectroscopy. Single-crystal X-ray analyses show that 1 has a centrosymmetric tetranuclear triorganotin selenite with a tetranuclear 16-membered macrocycle formed by trimethyltin and ligand alternately linking; 2 exhibits a 1-D neutral infinite chain structure in which the [O2SeC6H4-2-CF3]− is a μ2-bridging ligand; 3 and 4 are polymeric chain structures containing Sn2O4Se2 eight-membered rings where the areneseleninate groups are double bridges between the tin ions. Examination of the intermolecular contacts of 1 reveals the existence of the C–H⋯O hydrogen bonding interactions and C–H⋯π interactions. Weak C–H⋯O interactions were also found to be important for the formation of the 3-D structure for 3.

Syntheses and structural characterization of organotin(IV) complexes derived from reaction of 2,3-diphenylpropionic acid and various alkyltin salts

Five new organotin(IV) complexes, [(R3Sn)(O2C15H13)] n (R = Me: 1; nBu: 2), [RSn(O)(O2C15H13)]6 (R = Ph: 3), [(R2Sn)2(O2C15H13)2(μ 3-O)]2 (R = Me: 4), and [(R2Sn)(O2C15H13)2] (R = nBu: 5), have been prepared by the reaction of 2,3-diphenylpropionic acid and the corresponding organotin chloride with sodium ethoxide in methanol. All the complexes were characterized by elemental analysis, FT-IR, NMR (1H, 13C, 119Sn) spectroscopy, TGA, and X-ray crystallography. The structural analyses reveal that 1 and 2 are 1-D infinite polymeric chains with Sn in syn–anti conformation. Complex 3 has a drum structure with six Sn centers. Complex 4 has a supramolecular chain-like ladder through weak intermolecular Sn ··· O interactions. Complex 5 is a monomer, connected into a 1-D polymer through intermolecular C–H ··· O interactions. Complexes 1 and 5 crystallize in the orthorhombic space groups P212121 and P21212, which are chiral space groups.

Ligand-assisted assembly of polyoxozirconium clusters: syntheses and characterizations of tri- and tetranuclear half-zirconocene complexes

Two different polyoxozirconium oxide clusters tri- and tetranuclear half-zirconocene complexes assisted by 2,3,4,5-tetrafluorobenzoic acid and 3,4,5,6-tetrafluorophthalic acid have been synthesized and characterized by elemental analysis, FT-IR, NMR (1H, 19F, and 13C) spectroscopy, and X-ray crystallography. The structure analyses reveal that 1 is trinuclear with a µ3-oxygen bridge, central to a Zr–O backbone; 2 is a tetranuclear complex with four Zrs tetrahedrally arranged around a µ4-oxygen.