Syntheses,characterizations, and crystal structures of organotin(IV) chloride complexes with 4,4′‐bipyridine

The organotin(IV) chlorides R_nSnCl_4−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     

Syntheses, characterizations and crystal structures of triorganotin(IV) derivatives with 2-mercapto-4-quinazolinone

The triorganotin(IV) derivatives of 2-mercapto-4-quinazolinone (HSqualone) of the type, R₃SnL (R = Ph 1, CH₃2, PhCH₂3, p-F-PhCH₂4, o-F-PhCH₂5, n-Bu 6), were obtained by the reaction of the R₃SnCl and HSqualone with 1:1 molar ratio in benzene. All complexes 1-6 were characterized by elemental analyses, IR, ¹H and ¹³C NMR spectroscopy and the crystal structures of complexes 1-3 were also confirmed by X-ray crystallography. The structure analyses reveal that the tin atoms of complexes 1-3 are all distorted tetrahedral geometries. Furthermore, the dimeric structures in complexes 1-3 have also been found linked by intermolecular O-H?N or N-H?O hydrogen bonding interaction. Interestingly, the dimers of complexes 2 and 3 are further linked into one-dimensional chain through intermolecular C-H?S and C-H?O weak hydrogen bonding interactions, respectively.     

Syntheses and Crystal Structures of Benzyltin（Ⅳ） Derivatives of 2-Mercaptobenzothiazole

Introduction Metal thiolato complexes have been extensively investigated because of their ability to adopt various nuclearities and their relevance in biological science, since they form the inorganic part of the biologically active centers of some metalloproteins and enzymes.1-3 Recently, attention has been paid to the coordination chemistry of heterocyclic thiol/thione donors, which can give potential access to new compounds with unusual structures and reactivities,4 such as 2-mercaptobenzo-…     

Dichloro(4,4′‐dinonyl‐2,2′‐bipyridine‐κ2N,N′)platinum(II)

The title compound, [PtCl₂(C₂₈H₄₄N₂)], is a new square‐planar Pt^II complex con­taining a bi­pyridine moiety with two long alkyl‐chain substituents. The complex forms a segregated packing structure made up of the alkyl‐chain layers and paired coordination sites.     

Dimethyl 2,2′‐bipyridine‐6,6′‐dicarboxylate and bis(dimethyl 2,2′‐bipyridine‐6,6′‐dicarboxylato‐κ2N,N′)copper(I) tetrafluoroborate

The single‐crystal X‐ray structures of dimethyl 2,2′‐bipyridine‐6,6′‐dicarboxylate, C₁₄H₁₂N₂O₄, and the copper(I) coordination complex bis(dimethyl 2,2′‐bipyridine‐6,6′‐dicarboxylato‐κ²N,N′)copper(I) tetrafluoroborate, [Cu(C₁₄H₁₂N₂O₄)₂]BF₄, are reported. The uncoordinated ligand crystallizes across an inversion centre and adopts the anticipated anti pyridyl arrangement with coplanar pyridyl rings. In contrast, upon coordination of copper(I), the ligand adopts an arrangement of pyridyl donors facilitating chelating metal coordination and an increased inter‐pyridyl twisting within each ligand. The distortion of each ligand contrasts with comparable copper(I) complexes of unfunctionalized 2,2′‐bipyridine.     

Poly[μ8‐4,4′‐bipyridine‐2,2′,6,6′‐tetracarboxylato‐dilead(II)]

The Pb^II cation in the title compound, [Pb₂(C₁₄H₄N₂O₈)]_n, is seven‐coordinated by one N atom and six O atoms from four 4,4′‐bipyridine‐2,2′,6,6′‐tetracarboxylate (BPTCA⁴⁻) ligands. The geometric centre of the BPTCA⁴⁻ anion lies on an inversion centre. Each pyridine‐2,6‐dicarboxylate moiety of the BPTCA⁴⁻ ligand links four Pb^II cations via its pyridyl N atom and two carboxylate groups to form two‐dimensional sheets. The centrosymmetric BPTCA⁴⁻ ligand then acts as a linker between the sheets, which results in a three‐dimensional metal–organic framework.     

Syntheses and crystal structures of triorganotin(IV) complexes based on mixed ligands of 2,4,5-trifluoro-3-methoxybenzoic acid and 4,4′-bipy

Four new complexes have been synthesized based on the 2,4,5-trifluoro-3-methoxybenzoic acid and 4,4′-bipy of the type [R₃Sn(OOCC₆HF₃OCH₃)]₂·(4,4′-bpy). All complexes were characterized by elemental, IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectra analyses. Complexes 1 and 4 were also characterized by X-ray crystallography. Crystal structures of 1 and 4 show that the coordination number of tin atom is five and the 2D network is connected by intermolecular C–H···O interactions.     

Syntheses,characterizations and crystal structures of monomeric or macrocyclic compounds of di- or triorganotin (IV) moieties with 4,4′-thiodibenzenethiol

Six organotin compounds with 4,4′-thiodibenzenethiol (LH₂) of the type R_nSnL_4−nSnR_n (n = 3: R = Me 1, Ph 2, PhCH₂3, n = 2: R = Me 4, Ph 5, PhCH₂6) have been synthesized. All compounds were characterized by elemental analysis, IR and NMR (¹H, ¹³C, and ¹¹⁹Sn) spectra. The structures of compounds 1, 2, 4, 5 and 6 were also determined by X-ray diffraction analysis, which revealed that compounds 1 and 2 were monomeric structures, compounds 4, 5 and 6 were centrosymmetric dinuclear macrocyclic structures, and all the tin(IV) atoms are four-coordinated. Furthermore, supramolecular structures were also found in compounds 1, 2, 4, 5 and 6, which exhibit one-dimensional chains, two-dimensional networks or three-dimensional structures through intermolecular C–H?S weak hydrogen bonds (WHBs), non-bonded Sn?S interactions or C–H?π interactions.     

Cocrystallization of adamantane‐1,3‐dicarboxylic acid and 4,4′‐bipyridine

The cocrystallization of adamantane‐1,3‐dicarboxylic acid (adc) and 4,4′‐bipyridine (4,4′‐bpy) yields a unique 1:1 cocrystal, C₁₂H₁₆O₄·C₁₀H₈N₂, in the C2/c space group, with half of each molecule in the asymmetric unit. The mid‐point of the central C—C bond of the 4,4′‐bpy molecule rests on a center of inversion, while the adc molecule straddles a twofold rotation axis that passes through two of the adamantyl C atoms. The constituents of this cocrystal are joined by hydrogen bonds, the stronger of which are O—H...N hydrogen bonds [O...N = 2.6801 (17) Å] and the weaker of which are C—H...O hydrogen bonds [C...O = 3.367 (2) Å]. Alternate adc and 4,4′‐bpy molecules engage in these hydrogen bonds to form zigzag chains. In turn, these chains are linked through π–π interactions along the c axis to generate two‐dimensional layers. These layers are neatly packed into a stable crystalline three‐dimensional form via weak C—H...O hydrogen bonds [C...O = 3.2744 (19) Å] and van der Waals attractions.     

Wholly aromatic thermotropic liquid crystalline polyesters of 3,3′-bis(phenyl)-4,4′-biphenol with 4,4′-benzophenone dicarboxylic acid

A series of wholly aromatic, thermotropic polyesters, derived from 3,3′-bis(phenyl)-4,4′-biphenol (DPBP), nonlinear 4,4′-benzophenone dicarboxylic acid (4,4′-BDA), and various linear comonomers, were prepared by the melt polycondensation reaction and characterized for their thermotropic properties by a variety of experimental techniques. The homopolymer of DPBP with 4,4′-BDA had a fusion temperature (T_f) at 265°C, exhibited a nematic phase, and had a liquid crystalline range of 105°C. All of the copolyesters of DPBP with 4,4′-BDA and either 30 mol % 4-hydroxybenzoic acid (HBA), 6-hydroxy-2-naphthoic acid (HNA), or 50 mol % terephthalic acid (TA), 2,6-naphthalenedicarboxylic acid (2,6-NDA) had low T_f values in the range of 220–285°C, exhibited a nematic phase, and had accessible isotropization transitions (T_i) in the range of 270–420°C, respectively. Their accessible T_i values would enable one to observe a biphase structure. Each of the copolymers with HBA or HNA had a much broader range of liquid crystalline phase. In contrast, each of the copolymers with TA or 2,6-NDA had a relatively narrow range of liquid crystalline phase. Each of these polyesters had a glassy, nematic morphology that was confirmed with the DSC, PLM, WAXD, and SEM studies. As expected, they had higher glass transition temperatures (T_g) in the range of 161–217°C than those of other liquid crystalline polyesters, and excellent thermal stabilities (T_d) in the range of 494–517°C, respectively. Despite their noncrystallinity, they were not soluble in common organic solvents with the exception that the homopolymer and its copolymer with TA had limited solubility in CHCl₃. However, they were soluble in the usual mixture of p-chlorophenol/1,1,2,2-tetrachloroethane (60/40 by weight) with the exception of the copolymer with 2,6-NDA. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 769–785, 1997     

Syntheses, characterization and crystal structures of di- and triorganotin (IV) derivatives with 6-amino-1,3,5-triazine-2,4-dithiol

A series of organotin (IV) complexes with 6-amino-1,3,5-triazine-2,4-dithiol of the type [(R_nSnCl_4−n)₂ (C₃H₂N₄S₂)] (n = 3: R = Me 1, n-Bu 2, PhCH₂3, Ph 4; n = 2: R = Me 5, n-Bu 6, PhCH₂7, Ph 8) have been synthesized. All the complexes 1-8 have been characterized by elemental analysis, IR, ¹H and ¹³C NMR spectra. Among them complexes 1, 4, 5 and 8 have also been characterized by X-ray crystallography diffraction analyses, which revealed that the tin atoms of complexes 1, 4, 5 and 8 are all five-coordinated with distorted trigonal bipyramid geometries.     

Dichloro­(4,4′‐dialkyl‐2,2′‐bipyridine‐κ2N,N′)platinum(II), where alkyl is pentyl and heptyl

Dichloro­(4,4′‐dipentyl‐2,2′‐bipyridine‐κ²N,N′)platinum(II), [PtCl₂(C₂₀H₂₈N₂)], adopts a discrete π–π stacking structure, where the alkyl chains are located in a random manner. In contrast, dichloro­(4,4′‐diheptyl‐2,2′‐bipyridine‐κ²N,N′)platinum(II), [PtCl₂(C₂₄H₃₆N₂)], forms a layer structure comprised of alkyl chain layers and paired coordination sites, as observed for analogous complexes with longer alkyl chains.     

4,4′‐Bis(2,2,2‐trifluoroethoxymethyl)‐2,2′‐bipyridine

As part of a homologous series of novel polyfluorinated bipyridyl (bpy) ligands, the title compound, C₁₆H₁₄F₆N₂O₂, contains the smallest fluorinated group, viz. CF₃. The molecule resides on a crystallographic inversion centre at the mid‐point of the pyridine C_ipso—C_ipso bond. Therefore, the bpy skeleton lies in an anti conformation to avoid repulsion between the two pyridyl N atoms. Weak intramolecular C—H...N and C—H...O interactions are observed, similar to those in related polyfluorinated bpy–metal complexes. A π–π interaction is observed between the bpy rings of adjacent molecules and this is probably a primary driving force in crystallization. Weak intermolecular C—H...N hydrogen bonding is present between one of the CF₃CH₂– methylene H atoms and a pyridyl N atom related by translation along the [010] direction, in addition to weak benzyl‐type C—H...F interactions to atoms of the terminal CF₃ group. It is of note that the O—CH₂CF₃ bond is almost perpendicular to the bpy plane.     

Syntheses,crystal structures and blue emission of three zinc(II) coordination polymers with a 4,4′‐dicarboxybiphenyl sulfone ligand

Three novel zinc complexes [Zn(dbsf)(H₂O)₂] ( 1 ), [Zn(dbsf)(2,2′‐bpy)(H₂O)]·(i‐C₃H₇OH) ( 2 ) and [Zn(dbsf)(DMF)] ( 3 ) (H₂dbsf = 4,4′‐dicarboxybiphenyl sulfone, 2,2′‐bpy = 2,2′‐bipyridine, i‐C₃H₇OH = iso‐propanol, DMF = N,N‐dimethylformamide) were first obtained and characterized by single crystal X‐ray crystallography. Although the results show that all the complexes 1–3 have one‐dimensional chains formed via coordination bonds, unique three‐dimensional supramolecular structures are formed due to different coordination modes and configuration of the dbsf^2? ligand, hydrogen bonds and π–π interactions. Iso‐propanol molecules are in open channels of 2 while larger empty channels are formed in 3 . As compared with emission band of the free H₂dbsf ligand, emission peaks of the complexes 1–3 are red‐shifted, and they show blue emission, which originates from enlarging conjugation upon coordination. Copyright © 2006 John Wiley & Sons, Ltd.     

Poly[[trans‐diaquabis(μ2‐biphenyl‐2,2′‐dicarboxylato)bis(μ2‐4,4′‐bipyridine)dicobalt(II)] biphenyl‐2,2′‐dicarboxylic acid disolvate]

In the title compound, {[Co₂(C₁₄H₈O₄)₂(C₁₀H₈N₂)₂(H₂O)₂]·2C₁₄H₁₀O₄}_n, each Co^II ion is six‐coordinate in a slightly distorted octahedral geometry. Both Co^II ions are located on twofold axes. One is surrounded by two O atoms from two biphenyl‐2,2′‐dicarboxylate (dpa) dianions, two N atoms from two 4,4′‐bipyridine (bpy) ligands and two water molecules, while the second is surrounded by four O atoms from two dpa dianions and two N atoms from two bpy ligands. The coordinated dpa dianion functions as a κ³‐bridge between the two Co^II ions. One carboxylate group of a dpa dianion bridges two adjacent Co^II ions, and one O atom of the other carboxylate group also chelates to a Co^II ion. The Co^II ions are bridged by dpa dianions and bpy ligands to form a chiral sheet. There are several strong intermolecular hydrogen bonds between the H₂dpa solvent molecule and the chiral sheet, which result in a sandwich structure.     

Syntheses and fluorescence of salicylaldimine schiff base derivatives of 1,1′‐di(aminoethylaminocarbonylalkyl)‐2,2′‐biimidazole

The amide‐amine, 1,1′‐di(aminoethylaminocarbonylethyl)‐2,2′‐biimidazole (DAEPB) ( 1 ), and subsequent Schiff base imine product, 1,1′‐di(salicylaldiminoethylaminocarbonylethyl)‐2,2′‐biimidazole (DSEB) ( 2a ), have been synthesized from the ester, 1,1′‐di(ethoxycarbonylethyl)‐2,2′‐biimidazole (DEPB). Additionally, 1,1′‐di(salicylaldiminoethylaminocarbonylmethyl)‐2,2′‐biimidazole (DSMB) ( 2b ), was prepared from its corresponding amide‐amine. All compounds were characterized with FTIR, NMR and elemental analyses. The salicylaldimines, compounds ( 2a ) and ( 2b ), exhibit fluorescence at 540 and 520 nm, respectively, over a broad range of excitation wavelengths.     

Bis(4,4′‐bipyridinium) hexa­cyano­platinate(IV) bis­(4,4′‐bipyridine)

In the title compound, (C₁₀H₉N₂)₂[Pt(CN)₆]·2C₁₀H₈N₂ or [(Hbpy)⁺]₂[Pt(CN)₆]²⁻·2bpy, where bpy is 4,4′‐bipyridine, the Hbpy⁺ cations and bpy mol­ecules form a hydrogen‐bonded two‐dimensional cationic approximately square grid parallel to the (110) plane. The [Pt(CN)₆]²⁻ dianions reside in the cavities within this grid, with the nitrile N atoms forming weak hydrogen bonds with the CH groups in the cationic lattice.     

三元配合物钯（Ⅱ）-2,2''-联吡啶-L-天冬氨酸与DNA作用研究

The ternary complex Pd(Ⅱ)-2,2‘-bipyridine-L-asparagic acid was synthesized and characterized by elemental analysis, IR-spectra and molar conductance. The formula of the complex is Pd(bipy)(L-asp). The interaction of the complex with DNA has been studied by UV-spectra, fluorescence spectra, CD-spectra and gel electrophoresis. The results showed that the interaction of the complex with DNA performed mainly in intercalative mode and the extent of interaction was dependent on the concentration of the complex.     

Syntheses,characterizations and crystal structures of triorganotin(IV) complexes with amine derivatives of 6-amino-1,3,5-triazine-2,4-dithiol

Four new triorganotin(IV) complexes: Me₃SnL¹SnMe₃ (1), Ph₃SnL¹SnPh₃ (2), [Me₃SnL²] _n (3), Ph₃SnL²SnPh₃ (4) have been synthesized from 6-anilino-1,3,5-triazine-2,4-dithiol (L¹H₂) and 6-(dibutylamino)-1,3,5-triazine-2,4-dithiol (L²H₂). All were characterized by elemental analyses, IR and NMR spectra and X-ray diffraction analyses. Crystal structures show that 1, 2 and 4 are monomers with one ligand coordinated to two triorganotin moieties; complex 3 is a helical chain. Significant C–H ··· π, N–H ··· π interactions and intermolecular hydrogen bonds stabilize these structures.     

2,2′‐Diselenobis(4,4‐diphenylcyclohexa‐2,5‐dienone)

The title compound, C₃₆H₂₆O₂Se₂, displays crystallographic twofold symmetry. The packing involves corrugated linear ribbons mediated through C—H?O and C—H?Se inter­actions. The ribbons are connected through C—H?π inter­actions.