Formation and Structure of [Al_(13)(μ_3-OH)_6(μ_2-OH)_6(μ_2-OH)_(12)(H_2O)_(24)]Cl_(15)·13H_2O

1 INTRODUCTION At present, the polyaluminium compounds are mainly studied by single-crystal X-ray diffraction method to obtain the components, structures and exis- tence forms of aluminium in hydrolysis system, and then hydrolysis courses and mechanisms of each hydrolytic polyaluminium cation could be further dis- closed[1～5]. Generally, the single crystals suitable for X-ray diffraction are obtained from the crystallization of polyaluminium cations into sulfates or selenates. Following …     

CRYSTAL STRUCTURE OF (Br(μ-Met)(μ-Gly)(H_2O)_4]_2[Er(μ-Net)_2(H_2O)_4]_2(ClO_4)_(12)

<正> [Er(u-Met)(u-Gly)(H2O)4]2[Er(u-Met)2(HaO)4]2(ClO4)12(NMet=CH3S-(CH2)2CH(NH2)COOH,Gly=NH2CH2COOH), Mr=3194, trilinic, space group P1, a = 12.375(6),b= 14.041(13), c=19.074(13)A,α=80.85(6),β=80.72(6).γ=62.82(6)° ,Z=1,V= 2896A3,Dc=1.83 g/cm3,R=0.091. The carboxyl groups of Met and Gly in the title complex are bonded to Er atoms as bidentate bridging ligands.There are two different cations located at crystallographic symmetry centers in one unit cell.     

CRYSTAL STRUCTURE OF [Tm_4(p-NO_2C_6H_4CO_2)_(12)(H_2O)_(10)·2H_2O

<正> [Tm4 (p-NO2C6H4CO2)12 (H2O)10]·2H2O, Mr = 2885. 28, triclinic, space group P1 with a=14. 109(4) ,b= 14. 594(3) ,c= 13. 638(3) A ,α= 107. 04 (2), β=103. 36(2),γ= 93. 93(2)°, Z=1,V = 2584(1) A3.F(000) = l416,μ = 36. 4cm-1(Moka) ,Dc=1. 85g·cm3. The final R factor is 0. 034. The crystal structure is composed of tetrameric units in which four metal ions are bridged by carboxyl groups in chain form.     

Non-Isothermal Decomposion Kinetics of Supermolecule Compound [Eu(C_(10)H_9N_2O_4)(C_(10)H_8N_2O_4)(H_2O)_3]_2·phen·4H_2O

Europium(Ⅲ) compound with 2-oxopropionic acid salicyloyl hydrazone (C_(10)H_(10)N_2O_4,H_3L) and 1,10-phenan-throline (C_(12)H_8N_2,phen) has been prepared.A yellow prismatic crystal of the compound was obtained,and themolecule crystallized in the triclinic space group P-1.There are two 9-coordinated complex molecules in everystructure unit,where every Eu atom is coordinated by three water molecules and two tridentate C_(10)H_(10)N_2O_4 ligands,forming two stable pentacycles.The coordination polyhedron around Eu~(3+) was described as a single cap squareantiprism.In the crystal cell,there are one free 1,10-phenanthroline and four water molecules.The thermaldecomposition of the compound and its kinetics were studied by non-isothermal thermogravimetry.The Kissinger'smethod and Ozawa's method were used to calculate the activation energy value of the first-step decomposition.Thestages of the decompositions were identified by TG-DTG-DSC curve.The non-isothermal kinetic data were ana-lyzed by means of integral and differential methods.The possible reaction mechanism and the kinetic equationswere investigated by comparing the kinetic parameters.     

CRYSTAL STRUCTURE OF [Eu(μ-CH_3COC-O)(CH3COO)_2(H_2O)_2]_2·4H_2O

<正> C12H34O20Eu2,Mr=802.30 triclinic, space group P1, a= 8.955(2), b=9.328(1), c=10.536(2) A,α= 91.74(2),β=113.87(2),γ=118.23(2), V=681.7(2)A,Dm(flotation in CC14/ BrCH2CH2Br)=1.95,DX(Z=1) =1.954g cm-3,λ(MoKα)=0.71069 A,μ=6.41 cm-1,F(OOO)=391.92, T =. 295°K,final RF= 0.032 for 7483 observed reflections with |F0|>3a(|Fo|). The compound is isostructural with the known erbium complex,the basic unit being a centrosymmetric dimer composed of two nine-coordinate polyhedra sharing a common edge. An O atom in one or the three bidentate acetato groups about each europium atom serves as a bridge between the metal centars. The dimeric units are linked by hydrogen bonds involving both ligand and lattice water molecules to form a three-dimensional network.     

CRYSTAL STRUCTURE OF (C_5H_9C_5H_4)_3Er_4(μ_2-Cl)_6(μ_3-Cl)(μ_4-O)-(THF)_3

<正> The crystal of (C5H9C5H4)Er4(μ2-Cl)6(μ3-Cl)(μ4-O)(THF)3 belongs to triclinic space group P1, with a = 11. 909(4), b = 15.343(5), c=15. 619 (4)(?), α=104. 18(2), β=98. 81(3), γ= 111. 06(2)°, V = 2486(1)(?)3, Z = 2, Dc = 2. 07g/cm3, λ(MoKα) = 0.71073(?), μ= 73. 4cm-1, F(000) = 1476, Mr=1549. 25. The structure was solved by Patterson and Fourier techniques and refined by block diagonel least-squares method to final R = 0. 078 and Rw = 0. 084 for 5594 reflections with I≥1. 5σ(I). The results revealed that the complex is composed of four Er atoms bridged by seven Cl and one oxygen atoms with three of the Er atoms bonded each to a cyclopentylcyclopentadienyl group, and one Er atom, bonded to three THF. The Er atoms constitute a pseudo-tetrahedron.     

钴配合物[Co_2(H_2O)_8(C_(10)H_8N_2)_2]·(HO_3PCH_2CH_2SO_3)(SO_4)(H_2O)_4的合成与晶体结构研究

用硫酸钴、4,4'-联吡啶和2-磺酸基乙基膦酸合成了一个新颖的钴化合物:[Co_2(H_2O)_8(C_(10)H_8N_2)_2]·(HO_3PCH_2CH_2SO_3)(SO_4)(H_2O)_4,并对其进行了红外.元素分析、热重测试,通过单晶衍射仪测定了其晶体结构.结果表明,配合物属单斜晶系C2/c空间群,分子式为C_(22)H_(45)Co_2N_4O_(22)PS_2,分子量为930.57,晶胞参数为a=19.8456(18),b=11.2957(10),c=34.719(3)(A),β=106.095(3)°,晶胞体积为7477.9(12)(A)~3,Z=8,Dc=1.653 g/cm~3,F(000)=3856,μ=1.131 mm~(-1),最终残差因子R_1=0.0726,wR_2= 0.1719(相对于5612个I>2σ(I)的可观测衍射点).在这个化合物中,二齿配体4,4'-联吡啶把Co(II)桥连成[Co(4,4'-bipy)]~(2+)链.化合物中的[Co(4,4'-bipy)]~(2+)链有三个不同的朝向.2-磺酸基乙基膦酸没有参与配位而是做为一个有机模板剂填充在[Co(4,4'-bipy)]~(2+)链形成的空隙中.     

Synthesis and structures of novel octadecanuclear clusters [Cu_(12)RE_6(μ_3-OH)_(24)(pyb)_(12)(H_2O)_(18)(μ_(12)-ClO_4)]~(17+)(RE=Sm, Eu)

The novel octadecanudear Cu-RE cluster haw been isolated from the reaction system of aqueous Cu2+-RE3+-pyb (RE=Sm, Eu; pyb=pyridine betaine) and characterized by single-crystal structural analysis. The results show that the clusters comprise a [Cu12RE6(μ3-OH)24(μ12-ClO4)]17+ octahedral core, which encapsulates a ClO4- ion and has 18 water molecules and 12 bridging pyb carboxylato ligands as external ligands.     

Synthesis and Crystal Structure of Na_(10)[LaSiW_(11)O_(39)(H_2O)_4]_2·22H_2O

1 INTRODUCTION The pseudoliquid character of heteropoly compounds as catalysts is determined by their crystallographic properties. Study on the crystal structures of the heteropoly compounds could provide interesting information to enrich heteropoly acid and catalytic chemistry[1]. In the past, Zhuo Ying-Li抯 group has synthesized the carbamidine salts of 1:1 LnL(Ln=lanthanide, L=[SiW11O39]n－)[2], and Pope抯 group has reported that -SiW11O39 units are connected by lanthanide catio…     

Synthesis and structure of an open-type trinuclear molybdenum cluster compound[Mo_3(μ_3-S)(μ-S)_2-(μ-OAc)(S_2CNC_4H_8)_3(O)_2]·0.5CH_2Cl_2·2H_2O

The title compound was prepared by the reaction of Mo_3S_4(dtp)_4(H_2O)[ctp=S_2P(OEt)_2]with NaOAc·3H_2O and C_4H_8NCS_2NH_4.Crystallographic data:[Mo_3(μ_3-S)(μ-S)_2(μ-OAc)-(S_2CNC_4H_8)_3(O)_2]·0.5CH_2CI_2·2H_2O,Mr=980.18,triclinic,space group P,α=12.360(3),b=16.653(6),c=9.206(2)A,α=101.97(2),β=108.32(2),γ=86.14(3)°.V=1759.6(9)A~3,Z=2,Dc=1.85 g/cm~3,F(000)=962,μ(Mo K_α)=16.53 cm~(-1).Final R=0.044 for 4301 reflections with I≥3σ(I).This compoundmay be regarded as a mixed-valent trinuclear molybdenum cluster{Mo_2(V)Mo(Ⅳ)(μ_3-S)(μ-S)_2-(μ-OAc)(S_2CNC_4H_8)_3(O)_2}.The Mo-Mo distances are 2.783(1),2.833(1)and 3.374(2)A in the Mo_3non-equilateral triangle and there exist only two Mo-Mo bonds.The cluster was obtained by oxi-dation and ligand substitution of{Mo_3(μ_3-S)(μ-S)_3[μ-S_2P(OEt_2)][S_2P(OEt)_2]_3(H_2O)}.     

新型仲钨酸盐-B化合物[Na_2(H_2O)_(10)][Cu_4(H_2O)_(12)(H_2W_(12)O_(42))]·15H_2O体外抗肿瘤活性研究

对化合物[Na_2(H_2O)_(10)][Cu_4(H_2O)_(12)(H_2W_(12)O_(42))]·15H_2O(简称Na_2Cu_4W_(12))进行了体外抗肿瘤活性研究.应用四甲基偶氮唑盐(3-[4,5-dimethylthiazo-2-y]-2,5-diphenyltetrazolium bromide,MTT)比色法分析Na_2Cu_4W_(12)对人肝癌细胞(Hep G2)、人神经母细胞瘤细胞(SHY5Y)增殖抑制活性.采用光学显微镜观察肿瘤细胞的凋亡形态变化,用流式细胞术分析细胞周期和细胞凋亡,计算各期细胞比例及细胞凋亡率.结果表明,Na_2Cu_4W_(12)对Hep G2和SHY5Y 2种肿瘤细胞增殖半数抑制浓度IC_(50)值分别为5.3和10.2μmol·L~(-1),且呈剂量依赖性.光学显微镜下处理组细胞出现皱缩、变圆、缩小等形态变化,不同浓度Na_2Cu_4W_(12)处理12h早期凋亡细胞所占的百分比显著增加且呈剂量依赖性.综上所述,Na_2Cu_4W_(12)能够抑制胞瘤细胞增殖,诱导细胞凋亡.     

有机锡氧簇合物[(μ-O)(μ-OH)Sn_2(n-Bu)_4]_2(C_5H_4NCO_2)_2的合成、结构和量子化学研究

吡啶-4-甲酸与(n-Bu)2SnO反应合成二(μ-氧)二(μ-羟基氧)桥联四[二(正丁基)锡]二(吡啶-4-甲酸酯),经元素分析、1H NMR、IR和X-射线衍射表征分子结构,该配合物晶体属单斜晶系,空间群P21/n,晶胞参数:a=1.306 5(3)nm,b=1.314 5(2)nm,c=1.660 8(3)nm,β=96.180(5)°,V=2.835 7(9)nm3,Z=4,Dc=1.454 g.cm-3,μ(Mo Kα)=1.784 mm-1,F(000)=1 248,R1=0.044 9,wR2=0.124 1(I2σ(I))和R1=0.088 7,wR2=0.175 6(对所有的衍射)。共收集15 802个衍射点,其中独立衍射点4 885个,可观察衍射(I2σ(I))点2 733个用于结构精修。中心Sn原子形成五配位畸变三角双锥构型,分子间通过N…H-O氢键作用形成二维网络结构。利用量子化学G98W软件,在Lanl2dz基组对配合物的稳定性、前沿分子轨道组成及能量进行研究。     

Synthesis and Crystal Structure of Neodymium Heteropolymolybdate Complex Na_4(NH_4)_(10)[Nd_4 Mo_(29)O_(100)(H_2O)_(16)]·34H_2O

1INTRODUCT1ONThestudyofheteropolycomplexeshasbeenstartedmorethanonehundredyearsago.lnthepasttwentyyearstheheteropoly-coinplexesoftungstenandmolyb-denumhavebeenusedinpreparingcatalystfield,biologicalandionexchangemateri-als.Sothesecomplexeshavebeendeeplystudiedandexaminedbynewtechnicalmethodst2~7J.Wehavereportedthesynthesismethodandcrystalstructureoflanthanideele-mentneodymiumheteropolymolybdate(NH4),2H,,tNd'Mo,,O,,,(H,O)1,j.22H,O('i.Inthispaperwereportthesynthesismethodandcrystalstruc…     

Synthesis and Crystal Structure of LanthanideHetero-polymolybdate Complex:(NH_4)_(12)H_(10)〔Nd_4Mo_(29)O_(104)(H_2O)_(12)〕·22H_2O

11NTRODUCTIoNNowadaysheteropoly-complexesaremorenoticeableespeciallyinthefieldofcat-alystbecauseinsomeorganicsynthesestheycanbeusedasanoxidativetypeoracidictypecatalystorasboth.Ontheotherhandtherearemanytheoreticaltopicsaboutheteropolycomplexinwhichmanyscientistsareinterested.Inthefieldofpolyacidchemistrythesynthesisofanewheteropolycomplexisanimportantaspect.Molybdenumcanformbinaryheteropolymolybdatecomplexcompoundswithmanymetalandnon-metalelements.Indifferentcompoundstheratioofheteroatoms…     

Open-framework Borophosphate:(NH4)_(0.5)Fe~II_(0.5)Fe~III_(0.5)(H_2O)_2BP_2O_8·0.5H_2O

We are investigating the synthesis and properties of a new class of open framework borophosphate solids with the goal of being able to use in optical devices and magnetic materials. Only a few open-framework ferric borophosphate compounds with a chiral tetraheda-tetraheda helices, KFe(H2O)2BP2O8)H2O(1), Fe(H2O)2BP2O8H2O(2), (NH4)0.4-FeII0.55FeIII0.5(H2O)[BP2O8]0.6H2O(3) have been reported by Boy et al.1, Ylmaze et al.2 and Huang and Schfer et al.3. However, Huang and Schfer et…     

二核钒配合物NH_4[Gd(H_2O)_9][(VO)_2(μ_2-O)(nta)_2]的合成

以偏钒酸铵、氮三乙酸、氧化钆为原料,合成了新型钆修饰的二核钒配合物NH4[Gd(H2O)9][(VO)2(μ2-O)(nta)2][1, H3(nta)=氮三乙酸],其结构经UV, IR和元素分析表征.热稳定性测量显示,1在80 ℃以下能稳定存在.     

三核铬配合物[Cr_3(μ_3-O)(μ-OOCH)_6(OOCH)-(H_2O)_2]·3H_2O的晶体结构

标题三核铬配合物,C_7H_(17)Cr_3O_(20),M_r=577.2,属三斜晶系,空间群P,a=6.654(1),b=11.129(3),c=13.906(2),α=103.2188(3),β=103.5362(3),γ=92.0429(3)°;V=970.2(7) ~3。Z=2。D_c=1.976g.cm~(-3)。原子位置由直接法(MULTAN-82)和差Fourier法解出,经全矩阵最小二乘法精修,对于2801个I≥3σ(I)的独立衍射点,最后R=0.077。分子结构属于一般三核金属配合物构型,其显著特点是:有一个端基-HCOO单齿配位在一个Cr原子上,形成中性三核铬配合物。     

三价铬丙二酸配合物[Cr(C_3H_2O_4)(H_2O)_4][Cr(C_3H_2O_4)_2(H_2O)_2]·4H_2O的合成、晶体结构及性质研究

在三重桥氧三核铬羧酸配合物的系列研究中,采用与铬的一元羧酸配合物类似的实验条件,以丙二酸为配体合成了不同构型的配合物[Cr(C_3H_2O_4)(H_2O)_4)][Cr(C_3H_2O_4)_2(H_2O)_2]·4H_2O,通过X射线衍射测定了其单晶结构,并对-COO的配位方式作了讨论,还研究了配合物的红外光谱、拉曼光谱、紫外可见光谱、质谱、磁化率等性质,探讨了性质与结构的关系,并由此论证了二元羧酸和铬形成的双齿螯合构型化合物的稳定性.     

THE STRUCTURE OF TRIS(PYRIDINUM)(μ_3-SULFIDO)-TRIS(μ-DISULFIDO)-HEPTA-CHLORO-TRIMOLYBDENUM, (PyH)_3[Mo_3(μ_3-S)(μ-S_2)_3Cl_7]·1/2H_2O

<正> M=1101.86, cubic, Pa3, a=19.605(2), V=7533(3)A3, Z=8, Dc=1.943 g.cm-3. Final R=0.041 for 1120 reflections. The cluster anion is a mono(μ3-S) capped trinuclear species with each Mo atom having a distorted pentagonal bipyramidal coordination. A striking feature of this anion, which sharply differs from [Mo3S13] 2-,2 is the existence of a Cl atom connecting three S atoms by covalent bond to some extent.     

(NH_4)_(11)Gd[Gd_4Mo_(29)O_(100)(H_2O)_(16)]·33H_2O杂多化合物

苯二酚 ( DHB)是一种重要的化工原料 ,由苯酚过氧化氢羟化制苯二酚的生产路线 ,反应工艺简单 ,不污染环境 ,被认为是 2 1世纪最有价值、最有前途的工艺路线之一 .其关键在于研制高活性、高选择性的催化剂以提高产率使之实现工业化 .迄今为止 ,用于催化苯酚过氧化氢羟化制苯二酚的杂多化合物尚仅限于具有 Dawson结构的钼钒磷、钨钒磷杂多化合物[1,2 ] .本文设计合成了含稀土元素钆的二元杂多化合物 ( NH4 ) 11Gd[Gd4 Mo2 9O10 0 ( H2 O) 16]· 33H2 O,添加适量 V2 O5后应用于苯酚过氧化氢羟化制苯二酚反应 ,取得较好的催化效果 .称取 …