杂多化合物K_2HPMo_8W_4O_(40)·8H_2O的合成和结构

合成了Keggin结构的杂多化合物K2HPMo8W4O40·8H2O，并测定了其单晶结构。晶胞参数为：四方晶系，空间群92871073。该化合物是由和水分子组成。该阴离子属Keggin结构，其中的12个金属原子是Mo，W的统计分布。M-M（M=2／3Mo＋1／3W）的键长为3．54。     

[Cu(Bphe)_2(phen)]·H_2O的晶体结构

Cu（phen）Cl2与N-苯甲酰朱丙氨酸（Bphe）在水溶液中的取代反应生成了铜配合物[Cu（Bphe）2（phen）]·H2O。晶体属单科晶系，C2／c空间群。晶胞参数：a-5．330（1），分子计算式：mm－1。全矩阵最小二乘法修正，结构因子中心原子Cu与2个Bphe配体的O（3）、O（3A）及phen分子的2个N原子形成4配位的近似平面四边形结构。     

一种具有Keggin结构的固体杂多酸的合成及其晶体结构

以钨酸钠、氯化钴、醋酸钴及1,3-丙二胺为原料,利用水热合成法制备了一种具有Keggin结构的杂多酸H6[CoW12O40].2.5H2O;利用单晶X射线衍射分析了产物的晶体结构.结果表明,产物中的过渡金属Co2+离子作为中心原子与4个氧原子形成CoO4四面体;CoO4四面体被4个W3O13金属簇包围,与每个W3O13金属簇之间通过共顶点连接而形成[CoW12O40]6-阴离子;六个氢离子作为抗衡阳离子,最终形成固体杂多酸分子.     

新的夹层型杂多化合物（Hpy)_4Na_2H_2[Cu(H_2O){WO(H_2O)}(WO)-(AsW_9O_(33))_2·5H_2O的合成、性质和晶体结构

在pH=1.0的水溶液中，吡啶与Na12[Cu3(H2O)3(AsW9O33)2].xH2O反应，得到了 新的夹层型杂多钨酸盐（Hpy)4Na2H2[Cu(H2O){WO(H2O)}(WO)(AsW9O33)2].5H2O单 晶，用X射线单晶衍射法及元素分析确定了其结构，晶胞参数为：空间群P21/c, a=2.4681(5)nm,b=1.7474(3)nm,c=2.4853(5)nm,β=118.723(3)°，V=9.400(3) nm^3,Z=4,R1=0.0491,[Cu(H2O){WO(H2O)}(WO)AsW9O33)2]^8-是由两个a-B- AsW9O33^9-阴离子连接一个Cu^2+,两个W^6+形成的，中心离子的配位数分别为4， 5和6，讨论了标题化合物的形成条件。     

(enH_2)_5[(VO)_(12)O_6B_(18)O_(36)(OH)_6]·2(H_3O)·6H_2O的水热合成和晶体结构

以NH4VO3,H3BO3,乙二胺,MoO3,H2O为原料,按物质的量比2∶20∶9∶3∶222,在180℃条件下晶化,得到黑色棱形晶体(enH2)5[(VO)12O6B18O36(OH)6].2(H3O).6H2O.单晶结构分析结果表明该化合物属三斜晶系,Pī空间群,晶胞参数a=1.336 8(3)nm,b=1.599 8(3)nm,c=1.663 4(3)nm,α=94.040(1)°,β=91.530(1)°,γ=95.830(1)°,V=3.528 1(12)nm3,Z=2,Dc=2.099 g/cm3,μ=1.649 mm-1,F(000)=2 228,15 641个可观察独立衍射点射点(I>2σ(I)),最后结构精修到偏离因子R1=0.047 5,wR2=0.150 4,S=1.039.该化合物的结构主要由阴离子簇[(VO)12O6B18O36(OH)6]12-构成.该阴离子簇由B18O36(OH)6十八元环夹在两个以共边交替相连形成的V6O18簇中间,通过共用氧原子形成三明治式结构新颖的硼-钒-氧离子簇,簇间填充了一些(enH2)2+离子和水分子.     

含大环配体tacn的Co、Ni双金属配合物[Ni(tacn)_2]_2·[Co(dmg)_2Cl_2]_4·4H_2O的合成及晶体结构

标题化合物[Ni（tacn）2]2·[Co（dmg）2Cl2]4·4H2O（C56H112Cl8Co4N28Ni2O20）是由NiCl2·6H2O、CoCl2·6H2O、tacn·3HCl和dmg（丁二酮肟）在甲醇溶液中反应而得。结构通过经石墨单色器单色化的MoKα射线（λ=0.71073A）衍射法测定,共收集到16173个衍射点,其中独立衍射点14816个。解析结果表明,晶体属于三斜晶系,空间群为P1,晶胞参数为a=14.771（4）,b=18.297（5）,c=19.214（5）A,α=118.035（4）,β=97.545（5）,γ=91.273（5）°,V=4523（2）A3,Z=2。Mr=2102.48,Dc=1.544g/cm3,μ（MoKα）=1.435mm-1,F（000）=2176。晶体用直接法解出,经过最小二乘法对原子参数进行修正,最终的偏离因子为R=0.0884,wR=0.2239。分子中[Ni（tacn）2]2+阳离子和[Co（dmg）2Cl2]-阴离子间是通过静电才互作用结合在一起的。     

[Cu3(μ10-bta)(μ2-C2O4)(H2O)2]n的水热合成与结构表征

有机-无机杂化材料因其在催化、化学吸附、磁性和电子导体等方面具有广泛的应用而成为人们的研究热点[1,2]. 通过过渡金属离子和特殊的有机配体之间的反应, 一系列具有独特结构的配位聚合物已被合成出来. 多齿有机配体可螯合两个或多个金属离子, 这些金属离子之间存在良好的电子交换[3], 可形成一维、二维或三维的配位聚合物. 均苯三甲酸和均苯四甲酸都是良好的桥连多齿配体, Chui等采用均苯三甲酸合成了具有吸附作用的大孔道的[Cu3(tma)2(H2O)]n[4] (tma=benzene-1,3,5-tricarb-oxylate)三维配位聚合物, 并且[Ni(C12H3ON6O2)]3(tma)*H2O[5], [M(tma)2]*12H2O(M=Co,Ni,Zn)[6], Na2[Co(H2O)6(bta)]*4H2O[7] (bta=benzene-1,2,4,5-tetracarboxylate)和[Co(phen)(md)][8] (phen=1,10-phenanthroline, md=benzene-1,3-dicarboxylate)等配位聚合物也先后被合成出来.     

[(C_6H_5NO_2)Pr(H_2O)_4](CrMo_6O_(24)H_6)·(C_6H_5NO_2)·2.5H_2O的合成与晶体结构

用常规合成方法制备了基于Anderson结构阴离子的二维层状化合物[(C6H5NO2)2Pr(H2O)4](CrMo6O24H6)·2.5H2O,通过红外光谱和X射线单晶衍射对其进行了表征.结果表明,该化合物属于单斜晶系,C2/c空间群.a=2.3442(9)nm,b=1.3291(5)nm,c=2.458(1)nm,β=103.08(1)°,V=7.460(5)nm3,R1=0.0727,wR2=0.1903.结构分析表明,[CrMo6O24H6]3-阴离子通过端氧担载一个配位的Pr3+离子形成中性的(C6H5NO2)Pr(H2O)4(CrMo6O24H6)基团,相邻的中性基团在Ot—Pr—Ot桥联下形成一维链,链与链又通过异烟酸的桥联形成二维层状结构.     

一个新的超大铈锑钨酸盐阴离子Ce_3Sb_4W_2O_8(H_2O)_(10)(SbW_9O_(33))_4~(19-)

合成了一超大铈锑钨酸盐[Ce3Sb4W2O8（H2O）10（SbW9O33）4]（NH4）19·48H2O,用X射线单晶衍射法及元素分析确定了其结构.其晶胞参数为:α=1.890 8（6）nm,b=2.003 2（14）nm,c=2.865 3（12）nm,α=86.95（6）°,β=75.68（3）°,γ=67.52（5）°,υ=9.706（9）nm3,空间群P1.在杂多阴离子Ce3Sb4W2O8（H2O）10（SbW9O33）419-中,四个β-B-（SbW9O33）9-是通过一个大的中心集团[Ce3Sb4W2O8（H2O）10]17+连接起来的,中心集团中含有两个桥连{WO2-（H2O）}基,三个Ce（Ⅲ）离子和一个{Sb4O4}基团.三个Ce（Ⅲ）离子的配位数均为9,Ce（1）和 Ce（3）的配位环境相同,但不同于Ce（2）的配位环境,四个{SbW9O33}中的三个参与了向 Ce（Ⅲ）的配位.两个{SbW9O33}中的四个氧,三个水分子中的三个氧,{Sb4O4}中的一个氧及一个桥连{WO2（H2O）}中的一个氧向Ce（1）[或Ce（3）]配位;两个{SbW9O33}中的四个氧,两个水分子中的两个氧,{Sb4O4}中的一个氧及两个桥连{WO2（H2O）}中的两个氧向Ce（2）配位.在{Sb4O4}中,四个Sb原子的中心构成了一四面体.该离子属Cs点群,Sb（5）,Sb（8）和Ce（2）所在的平面是其对称面.     

三核锰配合物[Mn3O（O2CCHCICH3）6（py）2（H2O）]·2／3H2O的合成，晶体结构及磁性

用N-n-Bu4MnO4,醋酸锰,2-氯丙酸在无水乙醇溶剂中合成了三核锰配合物[Mn3O（O2CCHCICH3）6（py）2（H2O）]·2／3H2O（1·2／3H2O）。X-射线单晶衍射确定了其晶体结构。晶体属单斜晶系、C2／c空间群。3个Mn原子构成等腰三角形结构。变温磁化率研究表明配合物1存在反铁磁性交换作用。     

Synthesis and Structure of a POMs-based 3D Zeolike Ionic Crystal, {[Co（dpdo）2（H2O）2（CH3CN）]2（SiMo12O40）（H2O）2}n

A POMs-based 3D zeolike ionic crystal 1, {[Co（dpdo）2（CH3CN）（H2O）2]2（SiMo12O40）- （HEO）2}n （dpdo = 4,4＇-bipyridine-N,N＇-dioxide）, was constructed via self-assembly by embedding Keggintype [SiMo12O40]^4- polyanions within the intercrystalline voids as pillars and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with a = 11.430（3）, b = 12.242（3）, c = 14.279（3）A, α = 106.196（4）,β = 94.316（4）, γ = 98.294（3）°, V = 1884.5（7）A^3 Z = 1, C44H50N10O54CoEMo12Si, Mr = 2880.17, Dc = 2.538 g/cm^3, p = 2.484 mm^-1,F（000） = 1388, the final R = 0.0383 and wR = 0.1096 for 7753 observed reflections with I 〉 2σ（I）. Flack factor is 0.22（3）. Compound 1 is a pillar-layered framework with the [SiMo12O40]^4- anions linearly located on the square voids between the 2D bilayers which are formed by the dpdo ligands and cobalt（II） ions.     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ce(DMSO)_4(H_2O)_3Fe(CN)_6]·H_2O and [La(DMSO)_4(H_2O)_3Co(CN)_6]·H_2O(DMSO = Dimethylsulfoxide)

1INTRODUCTION Recently,cyano-bridged lanthanide-transition me-tal complexes have been extensively investigateddue to their potential applications as precursors in the preparation of rare earth orthoferrites,fluores-cent and magnetic materials[1].Various complexes of this system have been obtained in order to ex-plore the relations between structures and pro-perties by using different ligands,such as DMF,4,4?-bipy,and so on,to fill the coordination sites of lanthanide ions[2～9].But up to…     

A Novel 3D Extended Network Cobalt Paradodecatungstate:Synthesis,Characterization and Crystal Structure of [Co(H_2O)_5]_2[Co(H_2O)_4]_3[H_2W_(12)O_(42)]·11H_2O

1 INTRODUCTION Polyoxometalates are the unique metal-oxygen clusters composed of transition metals in groups V and VI (Mo, W, V, Nb, Ta) in a high oxidation state showing a large structural varieties as well as inte- resting physical and chemical properties in diverse fields including catalysis, analytical chemistry, nanotechnology, chemical sensing, biochemical and geochemical processes, medicine and materials science[1～5]. Recently, there has been increasing interest in the synthesis…     

CRYSTAL STRUCTRURE OF POTASSIUM BIS- (11-MOLYBDOSILICA-TO)DYSPROSATE(Ⅲ)

<正> Crystal of the title complex K10H3[Dy(SiMo11O39)2]·29H2O(Mr= 4331.85) is monoclinic with space group P21/n,a= 17. 256(1) ,b = 26. 817(1) ,c = 21.797(1) A,β= 104. 39(1)°, V = 9770. 2 (A3), Z= 4, F (000) = 8140, and Dc= 2. 94g/cm3. The Dy3+ is coordinated by eight oxygen atoms from two tetradentate (SiMo11O39)8- ligands,forming a square antiprism. The cation K+ is coordinated by oxygen atoms from heteropoly ligands (SiMo11O39)8- and water molecules, the number of atoms that are coordinated to the potassium atoms can be divided into four groups:six,seven, eight and nine.     

Syntheses and Crystal Structures of(H_3O)(C_3H_5N_2)[Mn(OH)_6Mo_6O_(18)]·3.5H_2O and (H_3O)_3[Co(OH)_6Mo_6O_(18)]·7H_2O

1 INTRODUCTION Polyoxometalates, a rich and remarkable classof inorganic cluster system[1], exhibit diverse appli-cation possibilities due to their topological and elec-tronic properties, ranging from their well-known roleas reagents in analytical, b…     

CRYSTAL STRUCTURE OF K_7H_6[Nd(GeMo_(11)O_(39))_2]·27H_2O

<正> K7H6[Nd(GeMo11O39)2]·27H2O, Mr = 4413.8, crystallizes in monoclinic, space group P21/n with a = 17. 095(4), b = 26. 895(3), c = 21. 214(5) (?); β=103. 11(2)°;V = 9499. 4(3)(?)3; F(000) = 8808; Z = 4; Dc = 3. 05g/cm3; μ(MoKα) = 43. 7cm-1 and λ=0. 71069(?). A total of 8644 reflections with I≥3σ(I) were used in the structure analysis. The final R value is 0. 090, Rw value is 0. 091. The atom Nd is situated between two tetradentate heteropoly (GeMo11O39)8- ligands to form the anion [Nd(GeMo11O39)2]13-. Nd is surrounded by eight oxygen atoms at average distances of 2. 446 (?), forming a square antiprism.     

CRYSTAL STRUCTURE OF (NH_4)_(11)[Na(H_2O)_2P_4W_(14)O_(58)] ·12H_2O

<正> (NH4)11[Na(H2O)2P4W14O58)·12H2O, Mr = 4099. 39, triclinic, space group P1, a = 14. 376(2), b = 19.861(9), c=13. 010(3)(?) , α=104. 68(2), β=91. 37(1), γ= 104. 05(2)°, V = 3471. 1 (?)3, Z = 2, Dc=3. 922g/cm3, μ (MoKα) = 238. 274cm-1, F(000) = 3664, R = 0.0510, Rw = 0. 0665 for 9260 observed reflections with I> 3σ(I). The polyanion [Na(H2O)2P4W14O58]11- consists of two PW7O29 subunits anisostructurally, two linkage phosphorous atoms and one sodium ion with two water ligands as well. The geometries of tungsten atoms within these two subunits are almost the same as those in K12P4W14O58· 21H2O[2]. The four phosphorous atoms are in PO4 coordinations. The sodium ion locates nearly at the center of the polyanion, and is coordinated by two water molecules, five oxygen atoms of the anion and one phosphorous atom with Na-P = 3. 053(3) (?). Due to the presence of the sodium atom, the interactions between oxygen and tungsten atoms in the polyanion are somewhat weakened.     

Synthesis, Crystal Structure and Luminescence Property of [Co(hmz)_2(H_2O)_4]·2H_2O

A new mononuclear Co(II) complex, [Co(hmz)2(H2O)4]·2H2O, has been synthesized by the reaction of Co(CH3COO)2·4H2O with 1-(4-hydroxyphenyl)-5-mercaptotetrazole (Hhmz). It crystallizes in the monoclinic system, space group P21/n with a = 13.502(5), b = 6.718(3), c = 13.972(6) , β = 117.532(4)o, V = 1123.9(8) 3, Z = 2, M r = 553.45, F(000) = 570, Dc = 1.635 g/cm3, μ = 1.008 mm–1, the final R = 0.0272 and wR = 0.0684 for 2194 observed reflections (I > 2σ(I)). The Co(II) is six-coordinated by two nitrogen atoms from two hmz–1 ligands and four water molecules, forming an octahedral geometry. The intermolecular hydrogen bonding and offset-panel π-π stacking interactions between the adjacent molecules extend the compound into a three- dimensional supramolecular framework. The title compound emits strong blue fluorescent light (λem(max) = 427 nm) at room temperature and is red-shifted compared with free ligand Hhmz (λem(max) = 342 nm).     

Synthesis and Crystal Structure of Co(C_6NO_2H_4)_3. H_2O

1INTRoDUCTIONAlotofresultsoncobaltcomplexstructureshavebeenreportedforseveraldecades.Theinterestofresearchinthisfieldhasneverbeenreducedbecausethecobaltcomplexesplayaveryimportantroleinthelifescienceandcatalysis,etc[1-6).WereportherethesynthesisandstructureofcomplexCo(C,NO,H'),.H,O.2EXPERIMENTALAllreagentsandsolventsusedareofARgradefromcommericalsourceswithoutfurtherpurification.ThetitlecompoundCo(C,NO,H,),.H,Owassynthesizedbythefollowingmethod.When2.4g(ca.1mmol)ofCoCl2.6H2Ow…     

Na_3H_2[PMo_(10)V_2O_(40)]·16H_2O的合成与晶体结构

标题化合物的晶体属P2_1/m空间群,α=13.821(2),b=15.355(3),c=11.597(2),β=107.50(2)°,V=2347.2~3,M_r=2091.46,Z=2,D_c=2.959 g·cm~(-3),μ(MoK_o)=30.77cm~(-1),F(000)=1992。用4049个独立可观测衍射精修结构,R=0.033。杂多酸阴离子[PMo_(10)V_2O_(40)]~(5-)具有准Keggin结构,12个金属原子呈无序分布,中心原子P与两个齿顶原子M(Mo/V)在对称面上。P—O平均键长1.541(2),M—O键长1.671(2)-2.432(2)。除一个Na—O配位多面体为畸变三方锥外,其余四个Na—O配位体均为六配位。讨论了Na~+离子呈无序分布的晶体结构特征并初步总结[PMo_(10)V_2O_(40)]~(5-)在不同晶相中的构型。