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1.
The crystal structure of the title compound, SnCl(C6H5)(C4H9)[S2CN(C2H5)2], was determined and refined to an R factor of 3.2% for 4876 reflections. The molecule contains five-coordinate tin in a distorted trigonal bipyramidal arrangement with the tin atom lying 0.20 Å below the equatorial plane formed by one of the sulphur atoms, S(1), and the donor carbons of the butyl and phenyl groups. The chlorine and the other sulphur atom, S(2), occupy axial sites, making a S(2)SnCl angle of 156.85(1)°. The SnS(2) bond is markedly elongated (2.764(1) Å) compared to the SnCl bond (2.449(1) Å) and the SnS(1) bond (2.454(1) Å). The structure resembles those of analogues such as (C6H5)2Sn(glygly) in having both hydrocarbon ligands located in the equatorial plane. Crystal data: space group P1: a = 8.291(2) Å, b = 14.726(3) Å, c = 9.509(2) Å, α = 96.24(2)°, β = 107.02(3)°, γ = 116.70(2)°, Z = 2, R = 3.2% for 4876 independent reflections.  相似文献   

2.
A series of cis-bis{5-[(E)-2-(aryl)-1-diazenyl]quinolinolato}di-n-butyltin(IV) complexes has been synthesized and characterized by 1H-, 13C-, 119Sn NMR, ESI-MS (electrospray ionization mass spectrometry), IR and 119mSn Mössbauer spectroscopic techniques in combination with elemental analyses. The structures of four di-n-butyltin(IV) complexes, viz., nBu2Sn(L3)2 (3), nBu2Sn(L4)2 (4), nBu2Sn(L5)2 (5) and nBu2Sn(L7)2 · 0.5C6H6 (7) (LH = 5-[(E)-2-(aryl)-1-diazenyl)quinolin-8-ol) were determined by single crystal X-ray diffraction. In general, the complexes were found to adopt a distorted cis-octahedral arrangement around the tin atom. These complexes retain their solid-state structure in non-coordinating solvent as evidenced by 119Sn and 13C NMR spectroscopic results. The in vitro cytotoxicity of di-n-butyltin(IV) complexes (3-8) is reported against seven well characterized human tumour cell lines. The basicity of the two quinolinolato donor N and O atoms of the ligands are discussed in relation to the cytotoxicity data.  相似文献   

3.
The crystal structure of isothiocyanatotriphenyl- (pyridinium-2-carboxylato)tin(IV) monohydrate is reported. The crystals are monoclinic, space group P21/n, a = 10.349(2), b =12.003(2), c = 19.325(4) Å, β = 97.68(2)°, Z = 4, refined to RF = 0.024 on 4249 observed reflections.The tin(IV) atom is five-coordinate, being bound to three phenyl groups, the isothiocyanato nitrogen atom and an oxygen from the picolinic acid. The geometry around the tin atom is trigonal bipyramidal, with the three phenyl groups occupying the equatorial positions, while the picolinic acid oxygen and the isothiocyanato nitrogen are coordinated axially. The acidic proton of picolinic acid has shifted position in the complex, and is bound to the heterocyclic nitrogen atom. The acid is thus coordinated in the form of a zwitterion. These trigonal bipyramidal units are linked together as dimers by pairs of water molecules, each of which hydrogen- bonds to the non-coordinated carboxylate oxygen atoms of both picolinic acid molecules, plus the heterocyclic nitrogen atom of one picolinic acid molecule. For complex formation with the protonated acid, theheterocyclic nitrogen should be alpha to the carboxylic acid group.  相似文献   

4.
Diorganotin(IV) complexes of N-acetyl-l-cysteine (H2NAC; (R)-2-acetamido-3-sulfanylpropanoic acid) have been synthesized and their solid and solution-phase structural configurations investigated by FTIR, Mössbauer, 1H, 13C and 119Sn NMR spectroscopy. FTIR results suggested that in R2Sn(IV)NAC (R = Me, Bu, Ph) complexes NAC2− behaves as dianionic tridentate ligand coordinating the tin(IV) atom, through ester-type carboxylate, acetate carbonyl oxygen atom and the deprotonated thiolate group. From 119Sn Mössbauer spectroscopy it could be inferred that the tin atom is pentacoordinated, with equatorial R2Sn(IV) trigonal bipyramidal configuration. In DMSO-d6 solution, NMR spectroscopic data showed the coordination of one solvent molecule to tin atom, while the coordination mode of the ligand through the ester-type carboxylate and the deprotonated thiolate group was retained in solution. DFT (Density Functional Theory) study confirmed the proposed structures in solution phase as well as the determination of the most probable stable ring conformation. Biological investigations showed that Bu2SnCl2 and NAC2 induce loss of viability in HCC cells and only moderate effects in non-tumor Chang liver cells. NAC2 showed lower cytotoxic activity than Bu2SnCl2, suggesting that the binding with NAC2− modulates the marked cytotoxic activity exerted by Bu2SnCl2. Therefore, these novel butyl derivatives could represent a new class of anticancer drugs.  相似文献   

5.
《Inorganica chimica acta》1988,150(2):279-285
Three new silver—tin complex salts with cis-1,2-bis(diphenylphosphino)ethylene have been synthesized. IR,31P and 119Sn NMR and conductivity data are reported and discussed together with the X-ray crystal structure of one of them, [Ag(cdppet)2][SnPh3(NO)3)2]. The silver atom is distorted tetrahedrally surrounded by the four phosphorus atoms of the two cdppet ligands. The tin atom is in a slightly distorted trigonal bipyramidal geometry with the phenyl carbon atoms in the equatorial plane and two oxygen atoms from monodentate nitrate groups at the apices.  相似文献   

6.
The interactions of the heteroallenes CO2, OCS, and CS2 with (Me2N)2Sn have been investigated. These CX2 species insert into the Sn-N bonds under mild conditions to provide products bis-(N,N-dimethylcarbamato)tin(II), [(Me2NCO2)2Sn]2, bis-(N,N-dimethylthiocarbamato)tin(II), [Me2NC(O)S]2Sn and bis-(N,N-dimethyldithiocarbamato)tin(II), (Me2NCS2)2Sn. These molecules have been fully characterized by traditional spectroscopic methods as well as by X-ray crystallography. The [Me2NC(O)S]2Sn product is the first example of a structurally characterized Sn(II) thiocarbamate. The solid-state structures of the final products vary depending on the heteroallene inserted. The CO2-inserted product is dimeric in the solid-state, with both bridging and chelating carbamate ligands. These dimers form a chain-like network via intermolecular Sn?O interactions. The monomeric thiocarbamate also shows a chain-like extended structure, through both Sn?O and Sn?S interactions, while the dithiocarbamate product has no significant intermolecular contacts.  相似文献   

7.
The crystal structure of chlorotriphenyl(quinolinium-2-carboxylato)tin(IV) monohydrate is reported. The crystals are monoclinic, space group C2/c with cell parameters a = 20.048(3) Å, b = 11.724(1) Å, c = 23.291(3) Å, ]gb = 113.42(1), Z = 8, refined to RF = 0.034 on 3331 observed reflections. The tin(IV) atom is five-coordinate, being found to three phenyl groups, the chlorine atom and an oxygen from the quinaldic acid. The geometry around the tin atom is trigonal bipyramidal, with the three phenyl groups occupying the equatorial positions, and the chlorine and quinaldic acid oxygen, the apical ones. The acidic proton of quinaldic acid has shifted position in the complex, and is bound to the heterocyclic nitrogen atom.The acid is thus coordinated in the form of a zwitterion. These trigonal bipyramidal units are linked together as dimers by pairs of water molecules, each of which hydrogen-bonds to the non-coordinated carboxylate oxygen atoms of both quinaldic acid molecules, plus the heterocyclic nitrogen atom of one quinaldic acid molecule. For complex formation with the protonated acid, the heterocyclic nitrogen should be alpha to the carboxylic acid group.  相似文献   

8.
The crystal structures of diacetatobis(thiourea)tin(II) (I) and ditin(II)tetrabromopenta(thiourea)dihydrate (II) have been determined by X-ray diffraction analysis. The compound I crystallizes in the monoclinic space group Pc with a = 11.932(6), b = 10.937(5), c = 21.919(8) Å, β = 96.5(1), Z = 8. The compound II crystallizes in the orthorhombic space group Pnma with a = 27.83(3), b = 16.13(4), c = 6.11(6) Å, Z = 4. In compound I the tin atom has a square pyramidal environment. It is bonded to two thiourea sulphur atoms and to two carboxylate oxygens. In the compound II there are two tin sites both with trigonal pyramidal coordination. The 119Sn Mössbauer data for thiourea tin(II) compounds are discussed, in terms of their crystal structures.  相似文献   

9.
A series of diorganotin (IV) complexes of the types of R2SnCl(SSCC3H3N2) (R = CH31, nBu 2, C6H53 and C6H5CH24), R2Sn(SSCC3H3N2)2 (R = CH35, nBu 6, C6H57 and C6H5CH28) and R2Sn(SSCC3H2N2) (R = CH39, nBu 10, C6H511 and C6H5CH212) have been obtained by reactions of 4(5)-imidazoledithiocarboxylic acid with diorganotin (IV) dichlorides in the presence of sodium ethoxide. All complexes are characterized by elemental, IR, 1H, 13C and 119Sn NMR spectra analyses. Also, the complexes 1, 7 and 9 are characterized by X-ray crystallography diffraction analyses, which reveal that the complex 1 is monomeric structure with five-coordinate tin (IV) atom, the complex 7 is monomeric structure with six-coordinate tin (IV) atom and the complex 9 is one-dimensional chain with five-coordinate tin (IV) atom.  相似文献   

10.
New organotin(IV) complexes of 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine (dbtp) and 5,7-diphenyl-1,2,4-triazolo[1,5-a]pyrimidine (dptp) with 1:1 and/or 1:2 stoichiometry were synthesized and investigated by X-ray diffraction, FT-IR and 119Sn Mössbauer in the solid state and by 1H and 13C NMR spectroscopy, in solution. Moreover, the crystal and molecular structures of Et2SnCl2(dbtp)2 and Ph2SnCl2(EtOH)2(dptp)2 are reported. The complexes contain hexacoordinated tin atoms: in Et2SnCl2(dbtp)2 two 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine molecules coordinate classically the tin atom through N(3) atom and the coordination around the tin atom shows a skew trapezoidal structure with axial ethyl groups. In Ph2SnCl2(EtOH)2(dptp)2 two ethanol molecules coordinate tin through the oxygen atom and the 5,7-diphenyl-1,2,4-triazolo[1,5-a]pyrimidine molecules are not directly bound to the metal center but strictly H-bonded, through N(3), to the OH group of the ethanol moieties; Ph2SnCl2(EtOH)2(dptp)2 has an all-trans structure and the C-Sn-C fragment is linear. On the basis of Mössbauer data, the 1:2 diorganotin(IV) complexes are advanced to have the same structure of Et2SnCl2(dbtp)2, while Me2SnCl2(dptp)2 to have a regular all-trans octahedral structure. A distorted cis-R2 trigonal bipyramidal structure is assigned to 1:1 diorganotin(IV) complexes. The in vitro antibacterial activities of the synthesized complexes have been tested against a group of reference pathogen micro-organisms and some of them resulted active with MIC values of 5 μg/mL, most of all against staphylococcal strains, which shows their inhibitory effect.  相似文献   

11.
The crystal structures of the title compounds Sb(C9H6NO)2(S2COC2H5) (1) and Sb(S2COC2H5)3 (2) have been determined by three dimensional X-ray diffraction techniques and refined by a least squares method; final R 0.049 for 2911 reflections [I ? 3σ(I)] for (1) and R 0.047, Rw 0.046 for 846 reflections [I ? 2σ(I)] for (2). Crystals of (1) are triclinic, space group P1, a = 10.825(2), b = 11.131(2), c = 8.911(1) Å, α = 109.45(1), β = 95.92(1) and γ = 93.02(1)° with Z = 2. Crystals of (2) are rhombohedral, space group R3, arhomb = 10.138(3) Å and α = 103.43(2)°. The environment of the Sb atom in (1) is based on a pentagonal bipyramidal geometry consisting of the six donor atoms of the three chelating ligands and a stereochemically active lone-pair of electrons which occupies the remaining axial position. The xanthate ligand chelates the Sb atom almost symmetrically with two long SbS bonds of 3.059(2) and 3.171(2) Å. In contrast the xanthate ligands in (2) chelate the Sb atom with asymmetric SbS bonds of 2.511(2) and 3.002(3) Å.  相似文献   

12.
A novel macrocyclic di-n-butyltin(IV) complex 1 was synthesized by the reaction of di-n-butyltin(IV) oxide and 2-mercapto-4-methyl-5-thiazoleacetic acid. Characterization of the complex 1 was achieved using elemental analysis, IR, 1H, 13C and 119Sn NMR spectra and X-ray diffraction. X-ray data of the complex 1 revealed that it is an unusual macrocycle containing the bridging-S-S-linkages and tetranuclear ladder based on a planar four-membered Sn2O2 ring. In the so-called ladder structure, there are two distinct tin environments, the endocyclic tin atom is best described as five-coordinate and the exocyclic tin atom as six-coordinate.  相似文献   

13.
The complexes [Me2(Meclo)SnOSn(Meclo)Me2]2 (2) and [Ph3Sn(Meclo)] (3) where HMeclo is meclofenamic acid, N-(2,6-dichloro-m-tolylanthranilic acid)], have been prepared and structurally characterized by means of vibrational, 1H and 13C NMR spectroscopies. The crystal structure of complexes (2) and (3) have been determined by X-ray crystallography. Three distannoxane rings are present to the dimeric tetraorganodistannoxane of planar ladder arrangement of (2). The structure is centro symmetric and features a central rhombus Sn2O2 unit two additional tin atoms linked at the oxygen atoms. Five- and six-coordinated tin centers are present in the dimer distannoxane. X-ray analysis of (3) revealed a penta-coordinated structure containing Ph3Sn coordinated to the chelated carboxylato group. The polar imino hydrogen atom participates in intra-molecular hydrogen bonds. Complexes (2) and (3) are self-assembled via π → π, C-H-π, stacking interactions and intra-molecular hydrogen bonds. Meclofenamic acid and [Ph3Sn(Meclo)] have been evaluated for antiproliferative activity in vitro against three human cancer cell lines: MCF-7 (human breast cancer cell line), T24 (bladder cancer cell line), A-549 (non-small cell lung carcinoma) and a mouse L-929 (a fibroblast-like cell line cloned from strain L). The [Ph3Sn(Meclo)] complex exhibited high cytotoxic activity against all the cancer cell lines. Meclofenamic and [Ph3Sn(Meclo)] were tested for anti-mycobacterial activity against Mycobacterium tuberculosis H37Rv. The [Ph3Sn(Meclo)] complex was found to be a promising anti-mycobacterial lead compound, displaying high activity against M. tuberculosis H37Rv.  相似文献   

14.
Reaction of di-n-butyltin(IV) dichloride with 4-chlorobenzohydroxamic acid at 1:1 ratio yielded a new mixed-ligand diorganotin(IV) complex, di-n-butyl-(4-chlorobenzohydroxamato)tin(IV) chloride(DBDCT). It was fully characterized by IR, 1H, 13C, 119Sn NMR spectra and single crystal X-ray analysis. In DBDCT, the tin atom is five-coordinated in a trigonal bipyramidal geometry. DBDCT exhibited strong in vitro cytotoxic activity toward human immature granulocyte leukemia (HL-60), human salivary-gland carcinoma (SGC-7901), human henrietta carcinoma (Hela) and human urinary bladder (T24) cell lines which, in some cases, were equal to, or even higher than those of cis-dichlorodiammineplatinum(II) (cisplatin, DDP), the widely clinically used drug. The further in vivo antitumor tests of DBDCT towards the transplantation tumor models of sarcoma carcinoma (S180), hepatocellular carcinoma (H22) and Ehrlich’s ascites carcinoma (EAC) on mice were carried out via injection intraperitoneally with cisplatin as positive contrast drug. The results showed that DBDCT displayed in vivo antitumor activity against the hepatocellular carcinoma H22 and sarcoma carcinoma S180 which were close to those of cisplatin, meanwhile, the survival-extending rates at middle dose and high dose on mice Ehrlich’s ascites tumor EAC were higher than those of cisplatin, and there was a good dose-effect relationship.  相似文献   

15.
The reaction of Sn(tmtaa)Cl2 (H2tmtaa=5,14-dihydro-6,8,15,17-tetramethyldi-benzo[b,i][1,4,8,11]tetraazacyclotetradecine) and ammonium thiocyanate or sodium azide under a mild condition resulted in trans six-coordinate tmtaa tin(IV) complexes, Sn(tmtaa)X2 (X=NCS, 1; X=N3, 2). However, the treatment of Sn(tmtaa)Cl2 and sodium picrate produced Sn(tmtaa)(Cl)(OC6H2 (2,4,6-3NO2)) (3). Only one chloro atom of Sn(tmtaa)Cl2 was substituted because of low nucleophilicity of the 2,4,6-trinitrophenolic anion in 3. Furthermore, because of the steric hindrance between the 2,4,6-trinitrophenolic group and the tmtaa ligand, which has a non-planar, saddle-shaped conformation, two chloro atoms cannot be substituted by two 2,4,6-trinitrophenolic groups simultaneously. All complexes were characterized by IR spectra, UV spectra, mass spectra, NMR spectra and elemental analyses, as well as DSC measurements. X-ray crystal structures of 1 and 3 reveal that the complexes retain the characteristic saddle-shaped configuration of H2tmtaa but have adopted the trans geometry. Solid state 119Sn NMR spectroscopy was used to study the bonding environment in the series of six-coordinate trans Sn(IV) tmtaa complexes. It can be found that the 119Sn chemical shifts of the Sn(IV) tmtaa complexes are almost not influenced by the substituents.  相似文献   

16.
《Inorganica chimica acta》1987,128(2):161-167
The complexes (Bu4N)[TcO(O2C6H4)2] (1) and Na[TcO(OCH2CH2O)2] (2) have been prepared by reacting TcOCl4- with respective diols in methanol. Compound 2 was identified by its elemental analysis and field desorption mass spectrum. Crystals of compound 1 are monoclinic, C2/c, with cell dimensions a = 10.393(3), b = 13.835(3), c = 20.643(5) Å, β = 101.74(3)° and four formula units in the unit cell. The crystal structure was determined by standard methods and refined to R1 = 0.0694, R2 = 0.0613, on the basis of 2887 independent reflections. The data were collected with use of Mo Kα radiation and a Syntex P21 diffractometer. The anion of 1 is square pyramidal with a short TcO(oxo) bond (1.648(5) Å). TcO distances to the diolate groups are longer (1.956(3), 1.958(3) Å). The technetium atom lies 0.7014(4) Å out of the plane of the four diolate oxygen atoms. Compound 2 is hydrolytically unstable in pure water, but can be stabilized by the addition of a several-fold molar excess of ethylene glycol. Compound 1 decomposes minimally in pure water after 24 h. These complexes are shown to be good structural models for 99mTc-radiopharmaceuticals containing purely oxygen-donor ligands. Comparison of the physical properties of the structurally characterized members of the series of complexes with core structures TcOSxO(4-x) (x = O, 2, 4) shows a shift to low energy in the frequency of the terminal oxygen-technetium band in the IR correlated with increasing softness of the basal plane donor atom set.  相似文献   

17.
Three types of methyltin phosphonates, {[(CH3)3Sn]4(O3PPh)2}n (1), {[(CH3)3Sn]2(O3PPh) · CH3OH}n (2) and {[(CH3)2SnO3PPh]4}n (3) were synthesized by the reaction of phenylphonic acid with trimethyltin (IV) chloride and dimethyltin (IV) dichloride, respectively. Complexes 1, 2 and 3 were characterized by elemental analysis, IR, NMR (1H, 13C, 31P and 119Sn) spectroscopy, TGA and X-ray crystallography diffraction analysis. The X-ray analysis of complex 1 shows that the structure is a polymeric infinite 1D zigzag chain. In complex 2, the oxygen atom of methanol molecule is coordinated to the tin atoms, and a 2D network is generated via O–H?O hydrogen bonds. In complex 3, a novel 2D network containing 12-membered (Sn3O6P3) rings is formed.  相似文献   

18.
《Inorganica chimica acta》1988,147(1):99-102
K2PtCl4 reacts with L-lysine and with D,L-diaminiopropionic acid (Dap) forming the neutral complexes [PtCl2(N,O-Lys)]·H20 (1) and [PtCl2(N,O-Dap)], (2) respectively.Compound 1 is monoclinic, space group P21 with a = 11.262(3), b = 11.041(2), c = 9.690(2) Å, β = 102.07(5)°, V = 1178(1) Å3 and Z = 4. Compound 2 is monoclinic, space group P21/n with a = 8.777(1), b = 10.615(2), c = 7.947(1) Å, β = 94.98(3)°, V = 738(1) Å3 and Z = 4. In both compounds, the zwitterionic ligands form an N,O-five membered chelate with the platinum atom. Structures 1 and 2 were refined to R values of 3.3% and 6.3% respectively.  相似文献   

19.
Fourteen di- and triorganotin(IV) derivatives with pentagonal bipyramidal and skew trapezoidal geometries have been synthesized and characterized. Dimethylstannyl bis[3-amino-4-chlorophenylcarboxylate] (1), bis[3-amino-4-chlorophenylcarboxylato] tetraethyldistannoxane] (2) and bis[3,5-dinitro-4-chlorophenylcarboxylato] tetra-n-butyldistannoxane (10) are dinuclear and tetranuclear complexes of bidentate ligands. The crystal structure of (1) is dimeric in which each Sn atom is seven coordinated. Study of weak intramolecular Sn?O interactions is very important to decide geometry around tin. Furthermore, it has been investigated that these compounds exhibit fairly good antibacterial, antifungal, cytotoxic, insecticidal and antiurease activities.  相似文献   

20.
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