Ge_(10)O_(28)单元构建的两个三维锗酸盐结构:(H_3O)_4Ge_7O_(16)·3H_2O和K_4Ge_9O_(20)

在半水溶剂热条件下 ,采用不同的合成条件合成了两个锗酸盐微孔分子筛 :(H3O) 4Ge7O16 ·3H2 O和K4 Ge9O2 0 .X射线单晶结构解析表明 ,两个晶体结构具有相同的“火箭状”二级结构单元 (SBU) ,SBU的不同的连接方式导致了完全不同的空间结构 .H4 Ge7O16 ·7H2 O的结晶学数据为Mr=894 2 7,P 43m ,a =0 7730 9( 18)nm ,V =0 462 0 5 ( 19)nm3,Z =1,MoKα ,λ =0 0 710 73nm ,R(F) =3 48% ,wR(F2 ) =8 39% .K4 Ge9O2 0 的结晶学数据为 :Mr=112 9 71,I4( 1) /a ,a =1 5 0 0 2 ( 3)nm ,c =0 7383( 2 )nm ,V =1 6618( 7)nm3,Z =4,MoKα ,R(F) =3 92 % ,wR(F2 ) =11 97% .     

九配位K_3[Ho(nta)_2(H_2O)]·5H_2O和八配位NH_4[Ho(cdta)(H_2O)_2]·4.5H_2O配合物的合成及结构

报道了稀土金属Ho~(III)离子氨基多羧酸（nta=氨基三乙酸,cdta=反式-1, 2-环乙二氨四乙酸）配合物的合成及分子结构和晶体结构的测定。具体结果如下： （a)分子式K_3[Ho(nta)_2(H_2O)]·5H_2O,单斜晶系,C2/c空间群,a = 1.5364 (8) nm, b = 1.2881(7) nm,c = 2.6163(13) nm, β = 96.140(9)°, V = 5. 416(5) nm~3,Z = 8,D_c = 1.932 g/cm~3, μ = 3.635 nm~(-1)和F(000) = 2944。其R和R_w值分别为0.0310和0.0675(对4509个独立的衍射点）,R和R_w值分 别为0.0442和0.0707（对所有10336个衍射点）。K_3[Ho(nta)_2(H_2O)]·5H_2O配 合物中,Ho~(III)N_2O_7部分是一个九配位单帽四方反棱柱体结构。(b)分子式 NH_4[Ho(cdta)(H_2O)_2]·4.5H_2O,三斜晶系,P1,空间群,a = 0.8636(3) nm, b = 1.0072(3) nm, c = 1.4457(5) nm, α = 88.382(5)°, β = 75.275(5)°, γ = 88.382(5)°, V = 1.2154(7) nm~3, Z = 2, D_c = 1.657 g/cm~3, μ = 3.315 nm~(-1)和F(000) = 606。其R和R_w值分别为0.0283和0.0708（对4203个独 立的衍射点）,R和R_w值分别为0.0325和0.0730(对所有4595个衍射点）。NH_4 [Ho(cdta)(H_2O)_2]·4.5H_2O配合物中Ho~(III)N_2O_6部分是一个八配位四方反 棱柱体结构。     

[Eu(C_(10)H_9N_2O_4)(C_(10)H_8N_2O_4)(H_2O)_3]·0.5bipy·3H_2O配合物的合成、晶体结构及荧光性质

在水-乙醇混合体系中,以2-羰基丙酸水杨酰腙(C_(10)H_(10)N_2O_4)、2,2-联吡啶(C_(10)H_8N_2,简写bipy)与Eu(NO_3)_3·4H_2O反应,首次培养出黄色单晶[Eu(C_(10)H_9N_2O_4)(C_(10)H_8N_2O_4)(H_2O)_3]·0.5bipy·3H_2O.该晶体属三斜晶系,空间群为P-1,晶胞参数a=0.93392(16)nm,b=1.3100(2)nm,c=1.3895(2)nm,α=97.205(3)°,β=105.411(2)°,γ=106.364(2)°,V=15.35(2)nm~3,Z=2,μ=2.118mm~(-1),Dc=1.686Mg/m~3,F(000)=786,R=0.0116,wR=0.0507,GOF=0.995.晶体测试结果表明,该单晶结构为铕的9配位配合物,两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位;每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C=N中的氮与Eu~(3+)配位,形成两个共边的稳定五元环,另三个配位原子则分别来自三个水分子中的氧原子,该配合物在空间呈扭曲的单帽四方反棱柱,而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子,这些游离分子与配位分子之间存在大量分子内和分子间氢键,整个分子在空间呈三维网状结构.发光性能测试表明该配合物具有很好的荧光性质.     

STRUCTURE OF POTASSIUM ∝-TRIVANADOENNEATUNGSTOGERMANATE ∝-K_3H_4 GeW_9 V_3 O_(40)·8H_2O

The complex K_3H_4GeW_9V_3O_(40)·8H_2O crystallized in a monocliinie system with space group P2, Mr=2784.67, a=11.099(3), b=16.452(4), c=13.534(4) , β=108.14°, Z=2,V=2348.49 ~3, F(000):2456, μ=239.7cm~(-1), De=3.932 g/cm~3. The final R=0.083 for 4528 non-zero reflexions. The structure of anions GeW_9V_3O_(40)~ and GeW_9O_(34)~ belongs to A--type.     

[(Sm(NMP)_4(H_2O)_4][HSiMo_(12)O_(40)]·2NMP·H_2O的合成、性质与晶体结构

在乙腈和水的混合溶剂中制得四水·四（N-甲基吡咯烷酮）合钐（III）配离 子与硅钼酸阴离子形成的复合物[Sm(NMP)_4(H_2O)4] [HSiMo_(12)O_(40)]·2NMP ·H_2O (NMP = N-甲基吡咯烷酮）,并对其进行了晶体结构测定。结构分析结果表 明该晶体属单斜晶系,P2_1/c空间群。晶胞参数α = 1.7501(4) nm, b = 1.8269 (4) nm, c = 2.3264(5) nm, β = 106.67(3)°,Z = 4, V = 7.126(2) nm~3, D_c = 2.457 g/cm~3, R = 0.0671, wR = 0.1635。结构测定结果表明,复合物中 Sm~(3+)与4个N-甲基吡咯烷酮和4个H_2O分子配位,以八配位的三角十二面体结构 阳离子通过静电作用与SiMo_(12)-O_(40)~(4-)阴离子相结合,分子中的质子氢存 在于两个游离的N-甲基吡咯烷酮的羰基氧之间。光照后复合物的低温ESR谱出现了 Mo~(5+)的顺磁信号,求得Mo~(5+)的g值为1.9447。热性质的研究表明,形成标题 化合物后,阴离子热稳定性增强。     

Synthesis and Fluorescent and Magnetic Properties of a New Europium Complex Eu(C_(20)H_(14)O_3N)_3(2,2'-bipy)(H_2O)·H_2O

A new europium(Ⅲ) complex Eu(C_(20)H_(14)O_3N)_3(2,2?-bipy)(H_2O)·H_2O has been synthesized with2-diphenylanine carbonyl benzoic acid and 2,2?-bipyridine as ligands.Crystal data for the complex are as follows:triclinic,space group ■,a=11.3334(5),b=16.0883(7),c=17.0116(8)?,α=70.411(4)o,β=82.435(4)o,γ=85.095(4)o,V=2894.0(2)?~3,D_c=1.484 g/cm~3,Z=2,μ=1.15 mm~(-1),F(000)=1320 and the final R=0.0447 and w R=0.0578.The Eu(Ⅲ) ion is coordinated by nine atoms to give a monocapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu~(3+):~5D_0→~7F_1 (592 nm) and ~5D_0→~7F_2 (616 nm),respectively.Also reported is the magnetic property of the complex.The complex exhibits antiferromagnetism in the temperature range of 300～2 K.     

Synthesis and the Fluorescent,Magnetic and Thermal Stability Properties of a New Terbium(Ⅲ) Complex Tb(C_(20)H_(14)O_3N)_3(C_(12)H_8N_2)(H_2O)·H_2O

A new terbium(Ⅲ complex Tb(C_(20)H_(14)O_3N)_3(C_(12)H_8N_2)(H_2O)·H_2O has been synthesized with 2-diphenylanine carbonyl benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: triclinic, space group P1, a =11.6034(6), b = 16.2465(8), c = 16.4427(8) ?, α = 73.168(5)o, β = 88.655(4)o, γ = 82.865(4)o, V = 2943.7(3) ?~3, Dc = 1.494 g/cm~3, Z = 2, μ(MoK α) = 1.272 mm~(-1), F(000) = 1348, the final R = 0.0535 and w R = 0.0809. The Tb(Ⅲ) ion is coordinated by nine atoms to give a monocapped square antiprism coordination geometry. The complex shows four fluorescence emission bands arising from the transitions of Tb~(3+): ~5D_4 → ~7F_6(491 nm), ~5D_4 → ~7F_5(546 nm), ~5D_4 → ~7F_4(585 nm) and ~5D_4→~7F_3(621 nm). Also reported are the magnetic and thermal stability properties of the complex.     

基于[As_2W_(19)O_(67)(H_2O)]~(14-)构筑的含镧砷钨酸盐的合成和结构表征

通过水热法合成了一例[As_2W_(19)O_(67)(H_2O)]~(14-)({As_2W_(19)})构型保持的稀土衍生物K_(14)H_8[La(H_2O)_3As_2W_(19)O_(67)(H_2O)]_2·53H_2O(1),并测定了其晶体结构.同时,通过红外光谱、粉末衍射(XRPD)以及热分析对其进行了表征.X射线单晶结构分析表明,化合物1属于三斜晶系,P-1空间群,晶胞参数为a=1.239 5(10)nm,b=1.847 8(16)nm,c=2.268 5(19)nm,α=68.366(12)°,β=78.215(13)°,γ=78.406(12)°,Z=1,Mr=11 351.63,V=4.683(7)nm3,μ=24.794mm-1,R1=0.056 4,wR2=0.150 8[I2σ(I)].化合物1是二聚结构,其中LaIII离子采用九配位畸变的单加冠四方反棱柱配位构型.     

CRYSTAL STRUCTURE OF 18-TUNGSTODIVANADATE ANION IN Na_2H_2[H_2V_2W_(18)O_(62)].12H_2O

The structure of Na_2H_2[H_2V_2W_(18)O_(62)]12H_2O has been determined by x-rayanalysis.The crystals are trigonal,space group R3m,with cell parametersa=37.613(11),c=12.972(7)A,V=15901(13)A~3,and Z=9.The structure model wasrefined by full-matrix least square to R=0.065 for 1702 reflections with F>4σ(F).The existence of the[H_2V_2W_(18)O_(62)]~(4-)heteropolyanion in the crystals has beenconfirmed.It is composed of two VO_4 tetrahedra and eighteen WO_6 octahedralinked to gve the Dawson-type structure.     

四面体磷酸镓和磷酸锗镓构成的新型—维链状分子筛结构

以1，3-丙二胺为模板剂，在溶剂热条件下合成了两个一维磷酸盐微孔分子筛 ：[GaP2O7(OH)][NH3(CH2)3NH3](1)和[Ge0.5GaP1.5O6.5(OH)1.5][NH3(CH2)3NH3] (2).X射线单晶结构解析表明，两个晶体结构分别由镓氧四面体和磷氧四面体，或 镓氧四面体，锗氧四面体和磷氧四面体组成，并沿层c轴方向形成链，这些链之间 由1，3-丙二胺相连，1的结晶学数据为Mr=331.82,P-1,a=0.8303(2)nm,b=0.8614 (3)nm,c=0.8880(2)nm,a=111.70(3)°,β=107.5(92)°,γ=98.39(2)°，V=0. 5382(3)nm^3,Z=1,MoKa,λ=0.071073nm,R(F)=5.56,wR(F^2)=14.36,2的结晶学数据 为：P2（1）/c,a=0.88968(7)nm,b=1.67562(13)nm,c=0.83666(7)nm,β=115.890 (2),V=1.12208(16)nm^3,Z=4,MoKa,R(F)=4.66,wR(F2)=10.10。     

Synthesis and Crystal Structure of K_8H_5［La（SiW_2Mo_9O_（39））_2（H_2O）_（17）］4H_2O

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆＫ_８Ｈ_５［Ｌａ（ＳｉＷ_２Ｍｏ_９Ｏ_（３９））_２（Ｈ_２Ｏ）_（１７）］４Ｈ_２ＯＬｕＢｉｎ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＨａｒｂｉｎＮｏｒｍａｌＵｎｉｖｅｒｓｉｔｙ，Ｈａｒ?..     

氰尿酸镍的晶体结构

标题化合物Ｎｉ（Ｃ＿３Ｈ＿２Ｎ＿３Ｏ＿３）＿２（Ｈ２Ｏ）＿４属正交晶系，空间群为Ｆｍｍｍ（编号６９）。晶胞参数：ａ＝７．２８２（４），ｂ＝１２．０５７（２），ｃ＝１６．０７２（２），Ｖ＝１４１１（１），Ｄ＿ｃ＝１．８２ｇ／ｃｍ￣３，Ｚ＝４，Ｍ＿ｒ＝３８６．８９，λ（ＭｏＫα）＝０．７１０６９，μ＝１４．４３ｃｍ￣（－１），Ｆ（０００）＝７９２。最终偏离因子Ｒ＝０．０４５，Ｒ＿ｗ＝０．０６０。独立可观测点数（Ｉ≥３σ（Ｉ））为３８５个。在配合物中，镍离子与来自氰尿酸的两个氮原子和来自水分子的四个氧原子配位。     

Synthesis and Structural Characterization of One New Polyoxotungstate Connected via Potassium Cations with aThree-dimensional Framework: H_6Na_2K_4(H_2W_(12)O_(42))Cl_2·14H_2O

One new polyoxotungstate complex H_6Na_2K_4(H_2W_(12)O_(42))Cl_2·14H_2O 1 has been prepared in the beaker solution and characterized by elemental analysis and IR spectroscopy. Crystal data: H36Cl2K4W12Na2O56, Mr = 3411.77, monoclinic, space group P21/c, a = 11.5734(16), b = 14.3136(19), c = 15.459(2) , β = 105.601(2)°, V = 2466.5(6)3, Z = 2, Dc = 4.594 g/cm3, F(000) = 3008, μ = 28.447 mm-1, R = 0.0574 and wR = 0.1239 (I > 2σ(I)). Single-crystal X-ray diffraction analysis results reveal that a three-dimensional architecture in the title compound is constructed from the H2W12O4210- units linked by potassium.     

超分子化合物[Ni(C_6H_4O_2N)_2·(H_2O)_4]_n的水热合成及晶体结构

用皮考林酸和六水合氯化镍反应制备了一种三维氢键超分子配合物,经X射线衍射分析确定了单晶结构.该晶体属单斜晶系,P21/m空间群,晶胞参数为:a=0.976 0(2)nm,b=0.522 54(10)nm,c=1.450 1(3)nm,Mr=374.98,α=90.08(3)°,β=90.08(3)°,γ=90°,V=0.739 63(3)nm3,Z=2,ρ=1.684 g/cm3,F(000)=388,μ=1.357 mm-1,R=0.039 0,wR=0.090 8.共收集2 656个衍射数据,其中1 569个为独立衍射点(Rint=0.033 2),可观测点数1 382个(I>2σ(I)).结果表明,在组成该超分子体系的基本结构单元[N i(C6H4O2N)2.(H2O)4]中,N i(Ⅱ)离子形成六配位的稍拉长的八面体构型,配合物单元之间通过氢键相互连接,形成了无限延伸的具有网状结构的三维超分子体系.     

咪唑配位的夹心型杂多化合物Na_9[{Na(H_2O)}_3{Co(C_3H_4N_2)}_3(BiW_9O_(33))_2]·33H_2O的合成，结构和磁性质研究

在pH=7.5的水溶液中，咪唑与Na_2WO_4,Bi(NO_3)_3及Co(NO_3)_2反应，得到 了咪唑配位的新型杂多钨酸盐Na_9[{Na(H_2O)}_3{Co(C_3H_4N_2)}_3(BiW_9O_(33) )_2]·33H_2O，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P3，a=1.3904(4)nm, b=1.3904(4)nm, c=3.3169(13)nm, γ=120 °,V=5.553(3) nm~3, Z=2, R_1=0.0361，wR_2=0.0507(I>2σ)。杂多阴离子[{Na(H_2O)_3}{Co (C_3H_4N_2)}_3(BiW_9O_(33))_2]~(9-)为夹心式结构，两个三空缺Keggin离子α- B-BiW_9O_(33)~(9-)夹层中的中心离子为交替排列的三个Na(H_2O)~+和三个Co (C_3H_4N_2)~(2+)，中心离子钴的配位数为5，该杂多阴离子具有C_(3v)对称性。 对标题化合物进行了磁性质表征，拟合结果为J=6.90cm~(-1),g=2.10,θ=0.25K， 表明该化合物中的Co(II)三核簇存在着铁磁偶合。     

A 3D Supramolecular Framework Based on 1D {[Co（proH）（H2O）3]2[P2Mo5O23]}n Chains and 1D Helical Water Chains

A three-dimensional supramolecular architecture, {[Co（proH）（H2O）3]2[P2Mo5O23]}·7H2O （1, pro = praline）, has been synthesized and characterized by IR, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. 1 crystallizes in monoclinic, space group C2 with a = 20.600（3）, b = 11.6980（11）, c = 9.2944（10）A, β = 107.837（4）°, V = 2132.1（4） A^3, Z = 2, C10H46Co2Mo5N2O40P2, Mr = 1493.99, Dc = 2.327 g/cm^3, F（000） = 1468, μ（MoKα） = 2.375 mm^-1, the final R = 0.0339 and wR = 0.0844 for 4169 observed reflections with I 〉 2σ（I）. Singlecrystal X-ray crystallographic analysis reveals that the helical water chains and {[Co（proH）- （H2O）3]2[P2Mo5O23]}n chains are perpendicular to each other and extend into an overall three-dimensional supramolecular architecture by hydrogen-bonding interactions. The magnetic investigation indicates weak antiferromagnetic interactions in the compound.     

新型环形聚阴离子[{WO(H_2O)}_3(AsW_8O31)_3]~21-的结构及表征

在pH=3.0的水溶液中，Na_2WO_4·2H_2O与NaAsO_2·6H_2O和NH_4Cl反应，得 到了新的杂多钨酸盐(MH_4)_19Na_2[{WO(H_2O)}_3(AsW_8O31)_3]·45H_2O单晶， 用X射线单晶衍射法及元素分析确定了其结构，晶体属单斜晶系，空间群C2/c，晶 胞参数为：a=3.1165(11)nm, b=1.7388(7)nm, c=2.2789(9)nm, β=97.342(6)°, V=12.248(8)nm~3, Z=4, R_1=0.0571,wR_2=0.0741[I＞2σ(I)]. 环型聚阴离子 [{WO(H_2O)}_3(AsW_8O31)_3]~21-是由三个{WO(H_2O)}桥连三个新发现的 {AsW_8O31}单元构成的，环聚离子[{WO(H_2O)}_3(AsW_8O31)_3]~21-具有近似D_ (3h)对称性。对该化合物还进行了~183W NMR, IR和TG表征。     

1,3-金刚烷二乙酸配体构筑的两个镉配合物的合成、表征及晶体结构

合成了2个一维Cd(Ⅱ)配合物[CdL(2,2′-bipy)]_n·nH₂O (1)和[CdL(2,2′-bipy)(H₂O)]_n·4nH₂O (2)(H₂L为1,3金刚烷二乙酸),并经X-射线单晶衍射方法测定了它们的晶体结构。在配合物1中,中心金属Cd(Ⅱ)为七配位的单帽三棱柱结构,而在配合物2中,Cd(Ⅱ)为七配位的五角双锥结构。1,3金刚烷二乙酸根作为桥联配体连接中心金属Cd(Ⅱ)离子形成一维链,同时通过氢键和π-π堆积作用形成三维超分子结构。研究了配合物1的荧光光谱。     

Synthesis,Structure and Electrochemical Property of a Supramolecular Compound（H2en）2[Cu（en）2（H3O）2][Mo8O28]

A supramolecular compound(H2en)2[Cu(en)2(H3O)2][Mo8O28](en=ethylenediamine) was hydrothermally prepared and confirmed by elemental analysis and TG analysis.Single-crystal X-ray analysis reveals that the crystal crystallizes in the triclinic system,space group P1 with a=9.4635(4),b=9.8645(5),c=10.9794(5),α=69.2050(10),β=72.3730(10),γ=78.4510(10)o,Mr=1559.55,V=908.24(7)3,Z=1,Dc=2.851 g/m3,F(000)=749,μ=3.350 mm-1,S=1.000,the final R=0.0217 and wR=0.0567.The compound consists of(H2en)2+,[Mo8O28]8-anion and [Cu(en)2(H3O)2]2+ cations and constructs a 3D supramolecular structure through hydrogen bonds between the nitrogen atoms from en of [Cu(en)2(H3O)2]4+ fragments and the terminal oxygen atoms from the [Mo8O28]8-polyoxoanions.The electrochemical behavior of this compound has been studied in detail based on a solid bulk modified carbon paste electrode of compound(CPE).     

(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.