2,5-二-(3,5-二甲基吡唑-4-巯基)-1,3,4-噻二唑-Cd(Ⅱ)配合物的合成、晶体结构及其抑菌活性

将配体Ll(2,5-二-(3,5-二甲基吡唑-4-巯基)-1,3,4-噻二唑)和L2(3,5-二甲基吡唑)同时与Cd(NO_3)_2·4H_2O进行配位反应,得到配合物[Cd(L1)_2(L2)(NO_3)_2(H_2O)],并用元素分析,FT-IR和X-射线单晶衍射进行了表征。晶体结构表明:配合物属于单斜晶系,P2_1/m空间群,每个Cd(Ⅱ)的配位环境为扭曲的五角双锥,分别与来自配体L1和L2的一个氮原子、两个硝酸根的三个氧原子、和一个水分子配位,配体L1只用一端的氮原子和Cd(Ⅱ)离子配位,配合物形成"E"字型结构。初步研究了配合物的体外抑菌活性,结果表明,配合物具有一定的抑菌活性。     

双核银配合物Ag_2[Ph_2P(CH_2)_2Ph_2]_4(NO_3·CH_3OH)_2的合成和分子结构研究

dppe配体按文献所示方法自行合成。在10ml甲醇中先后溶入0.05g(0.29mmol)AgNO_3和0.23g(0.58mmol)dppe。将过滤后的清液半敞开静置14天,即析出棱形无色晶体,再以甲醇重结晶。晶体由于溶剂化而极易风化成白色粉末。     

3-甲基-4-乙基-5-[2(或4)-吡啶基]-1,2,4-三唑银(Ⅰ)配合物的合成、晶体结构和光学性质

以3-甲基-4-乙基-5-（2-吡啶基）-1,2,4-三唑（L）和3-甲基-4-乙基-5-（4-吡啶基）-1,2,4-三唑（L''）为配体分别合成了2个银（Ⅰ）配合物[Ag₂（μ-L）₂L₂（NO₃）₂]（1）和{[Ag₂（μ-L''）₂（H₂O）₂]（NO₃）₂}_n（2）,测定了X射线单晶结构,用红外光谱、荧光和热重等进行了表征。2个配合物都属于三斜晶系,空间群为P1。晶体结构分析表明2个配合物都具有畸变的四面体结构[AgN₃O]。配合物1是一个双核银（Ⅰ）配合物,NO₃^-参与配位;而配合物2是一个配位聚合物,水分子参与配位。     

3-甲基-4-乙基-5-[2(或4)-吡啶基]-1，2，4-三唑银(Ⅰ)配合物的合成、晶体结构和光学性质

以3-甲基-4-乙基-5-（2-吡啶基）-1,2,4-三唑（L）和3-甲基-4-乙基-5-（4-吡啶基）-1,2,4-三唑（L''）为配体分别合成了2个银(Ⅰ)配合物[Ag2（μ-L）₂L₂（NO₃）₂]（1）和{[Ag₂（μ-L''）₂（H₂O）₂]（NO₃）₂}_n（2）,测定了X射线单晶结构,用红外光谱、荧光和热重等进行了表征。2个配合物都属于三斜晶系,空间群为P1。晶体结构分析表明2个配合物都具有畸变的四面体结构[AgN₃O]。配合物1.是一个双核银(Ⅰ)配合物,NO₃^-参与配位;而配合物2是一个配位聚合物,水分子参与配位。     

新型含2,5-二-（3,5-二甲基吡唑-4-巯基）-1,3,4-噻二唑-M(M=Co2+,Cd2+,Mn2+)配合物的合成、晶体结构及其抑菌活性研究

将配体L[2,5-二-(3,5-二甲基吡唑-4-巯基)-1,3,4-噻二唑]与Co(NO3)2 6H2O,Cd(NO3)2 4H2O和MnCl2 4H2O进行配位反应,得到三个配合物[Co(L)2(H2O)4](NO3)2 4(CH3CH2OH)(1),[Cd(L)2(H2O)4](NO3)2 4(CH3CH2OH)(2),[Mn(L)2(Cl)2(CH3OH)2]2(CH3OH)(3),并用元素分析,FT-IR和X射线单晶衍射进行了表征.分析结果表明,配体L呈"U"形,配合物1～3呈"S"形.配合物中Co(II),Cd(II),Mn(II)的配位环境均为扭曲八面体,每个金属离子同时和两个配体进行配位.配体和配合物体外抑菌活性研究结果表明,配体及其配合物都有一定的抑菌活性.     

2-氨基苯并噻唑配合物的晶体结构及抑菌活性

合成了2-氨基苯并噻唑与钴和锌的两种金属配合物,利用红外光谱、元素分析、X射线单晶衍射和热重分析等对其结构进行了表征;并研究了两种金属配合物对金黄色葡萄球菌、大肠杆菌、酵母菌的抑菌活性.结果表明,Zn(Ⅱ)和Co(Ⅱ)分别与2个O原子和2个N原子通过4配位形成扭曲的四面体构型;两种配合物对三种菌种均有较强的选择性抑制作用.     

联苯四甲酸及联吡啶构筑的一维链状银(Ⅰ)配合物的合成及晶体结构

采用水热法合成了一个新颖的配合物{[Ag(4,4′-bpy)][Ag2(H3btc)(H2btc)(4,4′-bpy)2].3H2O}n(1)(H4btc=联苯-2,2′,4,4′-四甲酸;4,4′-bpy=4,4′-联吡啶),并对其进行了元素分析、红外光谱和X射线单晶衍射测定。配合物1属于三斜晶系,空间群为P1,a=1.122 51(6)nm,b=1.554 01(8)nm,c=1.774 59(9)nm,β=91.641 0(10)°,V=2.830 8(3)nm3,Z=2,Dc=1.764 g.cm-3,μ=1.113 mm-1,F(000)=1 508,R1=0.045 0,wR2=0.086 2(I>2σ(I))。在1中,一维线性[Ag(4,4′-bpy)]+阳离子链包含在一维{[Ag2(H3btc)(H2btc)(4,4′-bpy)2]-阴离子双链与游离水分子通过分子间氢键组装成的三维超分子结构中。研究了配合物的热稳定性和电化学性质。     

两个由2-(4′-氯-苯甲酰基)苯甲酸构筑的铜、锌配合物的合成及晶体结构

通过水热法合成了2个新的配合物Cu2(cbba)4(phen)2(1)和Zn(cbba)2(bipy)(2)(Hcbba=2-(4′-氯-苯甲酰基)苯甲酸,phen=1,10-邻菲罗啉,bipy=2,2′-联吡啶),并对其进行了元素分析、红外光谱、热重和X-射线单晶衍射测定。这2个配合物通过π-π相互作用形成了三维超分子网状结构。此外,还研究了配合物2的荧光性质。     

硫脲壳聚糖-银配合物的制备及其结构和抑菌性能

合成了一系列不同银含量的硫脲壳聚糖-银配合物;利用傅立叶变换红外光谱分析了合成产物的结构,并测定了壳聚糖、硫脲壳聚糖及4种硫脲壳聚糖-Ag配合物对细菌和植物病原菌的抑菌性能.结果表明:硫脲壳聚糖-Ag配合物的抑菌性能优于单一的壳聚糖和硫脲壳聚糖;随着硫脲壳聚糖-Ag配合物中银含量的增大,抑菌效果明显增强.     

两个由2-(4′-氯-苯甲酰基)苯甲酸构筑的铜、锰配合物的合成及晶体结构

通过水热法合成了2个新的配合物[Cu(cbba)₂(im)₂] (1)和{[Mn(cbba)₂(bipy)(H₂O)₂]·bipy}_n(2)(Hcbba=2-(4′-氯-苯甲酰基)苯甲酸,im=咪唑,bipy=4,4′-联吡啶)。并对其进行了元素分析、红外光谱、热重和X-射线单晶衍射测定。这2个配合物通过氢键或π-π相互作用形成了三维超分子网状结构。     

A Novel Octahedral Hexasilver(I) Cluster: Ag_6[SSCN(n-C_4H_9)_2]_6

ＣｏｍｐｏｕｎｄｓｆｏｒｍｅｄｆｒｏｍＣｕ ,ＡｇａｎｄＡｕｗｉｔｈｄｉｔｈｉｏ ｌａｔｅｌｉｇａｎｄｓ ,ｓｕｃｈａｓｔｈｅｄｉａｌｋｙｌｄｉｔｈｉｏｃａｒｂａｍａｔｅ (ＤＴＣ) ,ｍｅｒｃａｐｔｏｔｈｉａｚｏｌｉｎｅ (ＨＭＴ)ａｎｄｄｉａｌｋｙｌｄｉｔｈｉｏｐｈｏｓｐｈａｔｅｓ(ＤＤＰ) ,ｈａｖｅｐｌａｙｅｄａｎｉｍｐｏｒｔａｎｔｒｏｌｅｉｎｔｅｃｈｎｏｌｏｇｙ .1Ｃｕ(Ｉ) Ｓｃｌｕｓｔｅｒｓａｌｓｏｈａｖｅｂｅｅｎｉｍｐｌｉｃａｔｅｄｉｎｂｉｏｌｏｇｙａｓａｎ ｔｉ ｏｘｉｄａｎｔｓ .2Ｔｈｅｃｕｂａｎ…     

A Novel Octahedral Hexasilver（I） Cluster： Ag[SSCN（n—C4H9）2]6

The first crystal structural report of a AgDTC complex (DTC-dialkyldithiocarbamate,R=n-butyl)presented in this paper shows that it is a hexanuclear species.The structural arrangement for the DDP(dialkyldithiophosphate)ligands is different from that of Cu6(DDP)6,but is the same as that of Ag6-[SSP(O-i-Pr)2]6.     

Novel 2-formylpyridine 4-allyl-S-methylisothiosemicarbazone and Zn(II), Cu(II), Ni(II) and Co(III) complexes: Synthesis,characterization, crystal structure,antioxidant, antimicrobial and antiproliferative activity

New zinc (II), copper (II), nickel (II) and cobalt (III) complexes, [Zn (HL)₂]I₂ (1) , [Cu (HL)Cl₂] (2) , [Cu (HL)Br₂] (3) , [Cu (HL)(H₂O)₂](ClO₄)₂ (4) , [Ni (HL)₂]I₂·H₂O (5) , [Co(L)₂]Cl (6) , [Co(L)₂]NO₃ (7) , [Co(L)₂]I·[Co(L)₂](I₃) (8) were obtained with 2-formylpyridine 4-allyl-S-methylisothiosemicarbazone ( HL ). The isothiosemicarbazone ligand was characterized by NMR (¹H and ¹³C), IR spectroscopy and X-ray diffraction. All the complexes were characterized by elemental analysis, IR, UV–Vis, ESI-MS spectroscopy, molar conductivity, magnetic susceptibility measurements. X-ray diffraction analysis on the monocrystal and powder elucidated the structure of the complexes 1 , 5 , 7 and 8 . The ligand and the complexes were tested for their antioxidant and antimicrobial activity against Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae and Candida albicans. Also, the antiproliferative properties of these compounds on human leukemia HL-60, human cervical epithelial HeLa, human epithelial pancreatic adenocarcinoma BxPC-3, human muscle rhabdomyosarcoma spindle, large multinucleated RD cells and normal MDCK cells have been investigated. The nickel complex 5 and cobalt complexes 6 , 7 showed promising antiproliferative activity and low toxicity.     

A new cyanobridged one-dimensional coordination polymer based on the octahedral rhenium cluster [Re6Se8(CN)6]4−: Synthesis and crystal structure of [{Cu(H2O)0.5(en)2} {Cu(en)2}Re6Se8(CN)6]·3H2O

The rhenium cluster complex [{Cu(H₂O)_0.5(en)₂} {Cu(en)₂} Re₆Se₈(CN)₆]·3H₂O has been obtained by the reaction of an aqueous solution of K₄[Re₆Se₈(CN)₆]·3.5H₂O with an aqueous solution of Cu(en)₂Cl₂ using cross diffusion through a gel. The structure of the compound has been characterized by a single-crystal X-ray diffraction method (a = 10.690(3) Å, b = 15.035(5) Å, c = 25.847(8) Å, V = 4154(2) ų, Z = 4, space group P2₁2₁2₁, R = 0.0651). Cluster anions [Re₆Se₈(CN)₆]^4? in the complex are connected with Cu²⁺ cations by cyano bridges resulting in zigzag chains. Coordination environment of cations is completed by ethylenediamine molecules. Additionally each cluster anion is coordinated by one terminal fragment {Cu(H₂O)_0.5(en)₂}.     

水杨醛双缩二氨基硫脲二丁基锡配合物的合成及杀菌活性研究

利用1,5-水杨醛双缩二氨基硫脲席夫碱与二丁基氧化锡为原料,在苯-甲苯混合溶剂中回流反应合成了有机锡席夫碱配合物,用元素分析、红外光谱、核磁共振谱对目标化合物结构进行了结构表征,并用X-射线单晶衍射对其结构进行了确证.晶体结构分析表明,标题配合物的晶体属三斜晶系,P-1空间群,每个独立单元中含有两个分子结构单元,晶胞参数:a=1.29705(6)nm,b=1.36654(7)nm,c=1.68517(8)nm,α=72.059(1)o,β=87.339(1)o,γ=63.435(1)o,V=2.5270(2)nm3,Z=4,Dcalc =1.433 g/cm3,μ=1.119 mm-1,F(000)=1112,R1=0.0563,wR2=0.1530.分子间经典的N-H...N氢键使分子相互缔合形成二聚体,后者再通过范德华作用力结合堆积形成完全的晶体结构.杀菌活性测定结果表明,标题化合物及其类似物的杀菌活性具有较大的选择性,对苏云金杆菌(B.thuringiensis)和枯草杆菌(B.Subtilis)的杀菌能力较高,而对大肠杆菌(E.Coli)和金黄色葡萄球菌(S.Aureus)的杀菌能力较低.     

Mono- and penta-nuclear self-assembled silver(I) complexes of pyrazolyl s-triazine ligand; synthesis,structure and antimicrobial studies

The self-assembled [Ag (PTDM)NO₃] ( 1 ), [Ag (PTDM)₂(H₂O)]ClO₄^.H₂O ( 2 ) and [Ag₅(PTDM)₄(H₂O)₆(ClO₄)₄]ClO₄^.2H₂O ( 3 ) complexes were synthesized by the direct mixing of AgX (X = NO₃¯ or ClO₄¯) and 4,4′-[6-(3,5-dimethyl-1H-pyrazol-1-yl)-1,3,5-triazine-2,4-diyl]dimorpholine ( PTDM ) ligand in water–methanol mixture. The coordination numbers of silver range from three to five. Complex 3 is a rare case in which one nitrogen atom from the same s-triazine core of the PTDM ligand has a μ(1,1) bridging mode between Ag1 and Ag2 in the penta-nuclear array with Ag1–N1 and Ag2–N1 distances of 2.666(4) and 2.418(3) Å, respectively. Its 3D topology has a kind of primitive dense packing derived from the α-Po type structure. Hirshfeld analysis showed that the percentages of the O^…H hydrogen bonds were 32.4, 25.4, and 42.0% in complexes 1 – 3 , respectively. While the ligand showed no antimicrobial activity at the applicable concentration, the penta-nuclear complex 3 had higher antibacterial (MIC = 3.7 μmol/L) and antifungal (14.6 μmol/L) potencies toward the tested microbes compared with complexes 1 and 2 . Also, the killing doses of 3 were in the range of 7.3–58.5 μmol/L compared with 18.2–291.1 and 20.1–160.6 μmol/L for 1 and 2 , respectively. It is clear that the higher Ag-content in 3 could be the main reason for its higher antimicrobial activity.     

配合物[1-(4′-bromo-2′-fluorobenzyl)pyridinium]2[Ni(mnt)2]和[1-(4′-bromo-2′-fluorobenzyl)pyrazinium]2[Ni(mnt)2](mnt2-=maleonitriledithiolate dianion)的合成及晶体结构

本文报道两个含双(马来二氰基二硫烯)镍(Ⅱ)配合物阴离子的离子对化合物。对阳离子为1-(4′-溴-2′-氟苄基)吡啶 盐时,生成配合物1。晶体数据:三斜晶系,空间P1群,a=0.7086(2)nm,b=1.0968(3)nm,c=1.1775(3)nm,α=69.914(5)°,β=89.495(5)°,γ=74.765(5)°,V=0.8259(4)nm³,Z=1。对阳离子为1-(4′-溴-2′-氟苄基)吡嗪鎓盐时,生成配合物2。晶体数据:单斜晶系,空间群P2₁/n,a=0.71554(17)nm,b=1.4262(3)nm,c=1.6725(4)nm,β=100.396(4)°,V=1.6788(7)nm³,Z=4。两个配合物中,阴离子为拟平面结构,镍原子均位于对称中心。变换对阳离子上的芳环种类对晶体的堆积结构产生影响。     

Synthesis and Crystal Structure of a Decanuclear Silver（I）-thiolate Compound Ag10S[S2P（OEt）2]8

A new decanuclear silver(I) compound Ag₁₀(μ₈‐S)(dtp)₈ [dtp=S₂P(OEt)₂] was isolated from a reaction mixture containing W₂S₄(dtp)₂ and AgN0₃, and its solid‐state molecular structure was determinated by X‐ray crystallography. The crystallographic study revealed that the compound contains a distorted mono‐capped quasi‐prism [Ag_io] with an octat‐bridging S atom at the center of the prism. The compound (C₃₂H₈₀Ag₁₀O₁₆P₈S₁₇, M_r=2592.46) crystallizes in the monoclinic P2₁/n space group, with a = 1.5111(5) nm, b=2.3656(8) nm, c=2.284(1) nm, β= 96.88(3)°, V=8.107(5) nm³, Z=4 and D,=2.12 g · cm^?3. The solution using direct method and full‐matrix least‐squares refinement led to R=0.066, Rw=0.078 for 3928 reflections with I3σ(I).     

Syntheses and Crystal Structures of Two New Iron-sulfur Carbonyl Complexes: [Fe2(SC6H4Cl)2(CO)6]·0.5(Et2O) and [Fe3(SC6H4NH2)6(CO)6]·2(MeOH)

Two new iron-sulfur carbonyl complexes, [Fe2(SC6H4Cl)2(CO)6]·0.5(Et2O) 1 and [Fe3(SC6H4NH2)6(CO)6]·2(MeOH) 2, have been prepared and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. Crystal data for 1: monoclinic, C2/c, a = 18.4439(8), b = 11.0999(5), c = 25.1830(10)(A), β = 97.0370(10)o, V = 5116.8(4)(A)3, Z = 8, C20H13Cl2Fe2O6.50S2, Mr = 604.02, Dc = 1.568 g/cm3, μ = 1.540 mm-1, F(000) = 2424, the final R = 0.0545 and wR = 0.1454 for 3443 observed reflections with I > 2σ(I); 2: monoclinic, P21/n, a = 12.350, b = 26.3050(11), c = 16.057(A),β = 97.891(3)°, V = 5166.9(2)(A)3, Z = 4, C44H44Fe3N6O8S6, Mr = 1144.76, Dc = 1.472 g/cm3, μ = 1.128 mm-1, F(000) = 2352, the final R = 0.0442 and wR = 0.1197 for 7978 observed reflections with I > 2σ(I). Complex 1 contains one iron dimer, in which two tricarbonyliron(I) fragments are bridged together by two 4-chlorophenylthiolate ligands, whereas complex 2 contains a linear tri-iron cluster, in which two terminal tricarbonyliron(II) fragments and the central Fe(II) atom are linked together by six 4-aminophenylthiolate bridging ligands.