一个新的超大铈锑钨酸盐阴离子Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)^1^9^-~4

合成了一超大铈锑钨酸盐[Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)~4](NH~4)~1~9.48H~2O,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：a=1.8908(6)nm,b=2.0032(14)nm,c=2.8653(12)nm,α=86.95(6)°,β=75.68(3)°,γ=67.52(5)°,V=9.706(9)nm^3，空间群P1。在杂多阴离子Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)^1^9^-~4中，四个β-B-(SbW~9O~3~3)^9^-是通过一个大的中心集团[Ce~3Sb~4W~2O~8(H~2O)~1~0]^1^7^+连接起来的，中心集团中含有两个桥连{WO~2(H~2O)}基，三个Ce(Ⅲ)离子和一个{Sb~4O~4}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{SbW~9O~3~3}中的三个参与了向Ce(Ⅲ)的配位。两个{SbW~9O~3~3}中的四个氧，三个水分子中的三个氧，{Sb~4O~4}中的一个氧及一个桥连{WO~2(H~2O)}中的一个氧向Ce(1)[或Ce(3)]配位；两个{SbW~9O~3~3}中的四个氧，两个水分子中的两个氧，{Sb~4O~4}中的一个氧及两个桥连{WO~2(H~2O)}中的两个氧向Ce(2)配位。在{Sb~4O~4}中，四个Sb原子的中心构成了一四面体。该离子属C~s点群，Sb(5),Sb(8)和Ce(2)所在的平面是其对称面。     

一个新的超大铈锑钨酸盐阴离子Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)^1^9^-~4

合成了一超大铈锑钨酸盐[Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)~4](NH~4)~1~9.48H~2O,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：a=1.8908(6)nm,b=2.0032(14)nm,c=2.8653(12)nm,α=86.95(6)°,β=75.68(3)°,γ=67.52(5)°,V=9.706(9)nm^3,空间群P1。在杂多阴离子Ce~3Sb~4W~2O~8(H~2O)~1~0(SbW~9O~3~3)^1^9^-~4中,四个β-B-(SbW~9O~3~3)^9^-是通过一个大的中心集团[Ce~3Sb~4W~2O~8(H~2O)~1~0]^1^7^+连接起来的,中心集团中含有两个桥连{WO~2(H~2O)}基,三个Ce(Ⅲ)离子和一个{Sb~4O~4}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{SbW~9O~3~3}中的三个参与了向Ce(Ⅲ)的配位。两个{SbW~9O~3~3}中的四个氧,三个水分子中的三个氧,{Sb~4O~4}中的一个氧及一个桥连{WO~2(H~2O)}中的一个氧向Ce(1)[或Ce(3)]配位;两个{SbW~9O~3~3}中的四个氧,两个水分子中的两个氧,{Sb~4O~4}中的一个氧及两个桥连{WO~2(H~2O)}中的两个氧向Ce(2)配位。在{Sb~4O~4}中,四个Sb原子的中心构成了一四面体。该离子属C~s点群,Sb(5),Sb(8)和Ce(2)所在的平面是其对称面。     

Imidazole Coordinated Sandwich-type Antimony Polyoxotungstates Na9[ {Na（H=O2}3{M（C3H4N2）}3（ Sb W9O33）2]·xH=O（M=Ni^Ⅱ, Co^Ⅱ, Zn^Ⅱ, Mn^Ⅱ）

The imidazole covalently coordinated sandwich-type heteropolymngstates Na9[ {Na（H=O2}3{M（C3H4N2）}3（ Sb W9O33）2]·xH=O（M=Ni^Ⅱ, Co^Ⅱ, Zn^Ⅱ, Mn^Ⅱ） were obtained by the reaction of Na2WO4·2H2O, SbCl3·6H2O, NiCl2·6H2O [MnSO4·H2O, Co（NO3）2·6H2O, ZnSO4·7H2O] and imidazole at pH≈7.5. The structure of Na9[{Na（H2O）2}3{Ni（C3H4N2）}3（SbW9O33）2]·32H2O was determined by single crystal X-ray diffraction. Polyanion [{Na（H2O）2}3{Ni（C3H4N2）}3（SbW9O33）2}3]^9- has approximate C3v symmetry, imidazole coordinated six-nuclear duster [{Na（H2O）2}3{Ni（C3H4N2）}3]^9＋ is encapsulated between two （α-SbW9O33）^9-, the three rings of imidazole in the polyanion are perpendicular to the horizontal plane formed by six metals （Na-Ni-Na-Ni-Na-Ni） in the central belt, and x-stacking interactions exist between imidazoles of neighboring polyanions with dihedral angel of 60%. The compounds were also characterized by IR, UV-Vis spectra, TG and DSC, and the thermal decomposition mechanism of the four compounds was suggested by TG curves.     

新型有机-无机杂化的类Dawson型多金属钨酸盐[Co(2,2′-bpy)_3]_2[Co(2,2′-bpy)_2Cl][Co(2,2′-bpy)_2]H_2-[SbW_(18)O_(60)]·4H_2O的合成、晶体结构及性质

以Sb2O3、Na2WO4、CoCl2及2,2′-联吡啶为原料,采用水热合成方法,制得了新颖的有机-无机杂化的类Dawson型多金属氧酸盐:[Co(2,2′-bpy)3]2[Co(2,2′-bpy)2Cl][Co(2,2′-bpy)2]H2-[SbW18O60]·4H2O(2,2′-bpy=2,2′-bipyridine),并通过元素分析,IR,XPS,EPR,TG,变温磁化率和X-射线单晶衍射等分析手段对化合物进行表征.X-射线单晶衍射测定表明,该化合物属于正交晶系,Pba2空间群,晶胞参数:a=2.1208(2)nm,b=2.4506(2)nm,c=1.2931(1)nm,Z=2,R1=0.0416,wR2=0.0771.晶体解析表明,Sb2O3与Na2WO4在水热条件下组装成少见的类Dawson型多金属氧酸盐阴离子[SbW18O60]9-,该阴离子的{W18}簇结构骨架中包含一个三角锥形{SbO3}基团.EPR谱分析表明,高自旋态和低自旋态Co2 共存于标题化合物中.磁性质研究表明标题化合物显示抗磁性.     

Synthesis, crystal structure and properties of a new organic-inorganic hybrid Dawson-like polyoxotungstate [Co(2,2′-bpy)_3]_2[Co(2,2′-bpy)_2Cl][Co(2,2′-bpy)_2]H_2- [SbW_(18)O_(60)]·4H_2O

A new organic-inorganic hybrid polyoxometalate based on Dawson-like polyoxotungstate anion [SbW18O60]9, formulated [Co(2,2′-bpy)3]2[Co(2,2′-bpy)2Cl][Co(2,2′-bpy)2]H2[SbW18O60]·4H2O (2,2′-bpy= 2,2′-bipyridine) has been synthesized from Sb2O3, Na2WO4, CoCl2, and 2,2′-bipyridine materials by hydrothermal method, and which was characterized by elemental analyses, IR, XPS, EPR, TG, and X-ray single crystal diffraction. Structure analysis shows that the polyoxoanion self-assembled under hydrothermal conditions consists of a Dawson-like polyoxotungstate cluster anion [SbW18O60]9 en- capsulating a pyramidal {SbO3} group within the {W18} cluster cage. EPR spectra show that the high-spin octahedral CoII and low-spin CoII ions coexist in the title compound. Magnetic properties in- dicate that the compound is antiferromagnetic.     

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。     

一个新的铈砷钨酸盐大阴离子[As4W40O140Ce(H2O)5]^25-

合成了一新的铈砷钨酸盐[As4W40C140Ce(H2O)5]Na25·63H2O,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：a=3.1252(8)nm,b=2.2656(6)nm,c=1.3973(9)nm,α=β=γ90°,V=9.893(7)nm^3,空间群P21/m21/m2/n。在聚阴离子[As4W40O140Ce(H2O)5]^25-中,四个桥连WO6八面体通过相互共享两个顺式氧串联四个B-α-(AsW9O33)^9-形成环配体(As4W40O140)^28-的基本框架,四个B-α-(AsW9O33)^9-并不处在一个平面上,而是上下交错分布的。中心离子Ce(Ⅲ)未完全填充在(As4W40O140)^28-中具有八齿配位能力的S1洞穴中,而是四个桥连的WO6八面体各提供一个端基氧向Ce(Ⅲ)配位,另有五个水分子向Ce(Ⅲ)配位,Ce(Ⅲ)离子的配位数为9,该离具有C2v对称性。     

吡啶配位的夹心型杂多阴离子{[Na(H2O)2]3[Ni(C5H5N)]3(AsW9O33)2}9-的结构及磁学性质

The pyridine coordinated sandwich-type heteropolytungstate Na7[Ni（H2O）6] { [Na（H2O）2]3[Ni（C5H5N）]3（AsW9O33）2}·28H2O was obtained by the reaction of Na2WO4·2H2O, NaAsO2 and pyridine with NiCl2·6H2O at pH =7.0 and characterized by elemental analysis, IR, UV-Vis,^1H NMR spectra and magnetic measurement. The structure of this heteropolytungstate was determined by X-ray diffraction analysis, which crystallized in triclinic system, space group P1 with a= 1.3153（9） nm, b= 1.7228（12） nm, c=2.6866（19） nm, a=74.130（11）°,β=78.032（12）°, γ = 73.179（12）° and Z= 2, R1 = 0.0604, wR2 = 0.0915 [I〉 2σ（I）]. Polyanion {[Na（H2O）2]3[Ni（C5H5N）]3（AsW9O33）2}^9- has approximately C3 symmetry, and three pyridine coordinated Ni（C5H5N）^2＋ and three Na（H2O）2^＋ are encapsulated between two AsW9O33^9- . Magnetic measurements show that central Ni3 unit in the polyanion exhibits ferromagnetic Ni-Ni exchange interactions （J=6.17 cm^-1）.     

新型有机-无机杂化的类Dawson型多金属钨酸盐[Co(2,2''-bpy)3]2[Co(2,2''-bpy)2Cl][Co(2,2''-bpy)2]H2[SbW18O60]·4H2O的合成、晶体结构及性质

以Sb2O3、Na2WO4、CoCl2及2,2′-联吡啶为原料, 采用水热合成方法, 制得了新颖的有机-无机杂化的类Dawson型多金属氧酸盐: [Co(2,2′-bpy)3]2[Co(2,2′-bpy)2Cl][Co(2,2′-bpy)2]H2- [SbW18O60]·4H2O (2,2′-bpy = 2,2′-bipyridine), 并通过元素分析, IR, XPS, EPR, TG, 变温磁化率和X-射线单晶衍射等分析手段对化合物进行表征. X-射线单晶衍射测定表明, 该化合物属于正交晶系, Pba2空间群, 晶胞参数: a = 2.1208(2) nm, b = 2.4506(2) nm, c = 1.2931(1) nm, Z = 2, R1 = 0.0416, wR2 = 0.0771. 晶体解析表明, Sb2O3与Na2WO4在水热条件下组装成少见的类Dawson型多金属氧酸盐阴离子[SbW18O60]9-, 该阴离子的{W18}簇结构骨架中包含一个三角锥形{SbO3}基团. EPR谱分析表明, 高自旋态和低自旋态Co2+共存于标题化合物中. 磁性质研究表明标题化合物显示抗磁性.     

Synthesis, crystal structure and properties of a new organic-inorganic hybrid Dawson-like polyoxotungstate [Co(2,2''''-bpy)3]2[Co(2,2''''-bpy)2Cl][Co(2,2''''-bpy)2]H2-[SbW18O60]·4H2O

A new organic-inorganic hybrid polyoxometalate based on Dawson-like polyoxotungstate anion [SbW18O60]9-, formulated [Co(2,2'-bpy)3]2[Co(2,2'-bpy)2Cl][Co(2,2'-bpy)2]H2[SbW18O60]·4H2O (2,2'-bpy= 2,2(-bipyridine) has been synthesized from Sb2O3, Na2WO4, CoCl2, and 2,2'-bipyridine materials by hydrothermal method, and which was characterized by elemental analyses, IR, XPS, EPR, TG, and X-ray single crystal diffraction. Structure analysis shows that the polyoxoanion self-assembled under hydrothermal conditions consists of a Dawson-like polyoxotungstate cluster anion [SbW18O60]9- encapsulating a pyramidal {SbO3} group within the {W18} cluster cage. EPR spectra show that the high-spin octahedral CoⅡ and low-spin CoⅡ ions coexist in the title compound. Magnetic properties indicate that the compound is antiferromagnetic.     

［Vmo_3O_4（O_2CEt）_8］_2Na_2的合成与结构

［ＶＭｏ３Ｏ４（Ｏ２ＣＥｔ）８］２Ｎａ２（１），三斜晶系，Ｐ１空间群，ａ＝１２．９７７（７），ｂ＝１４．０７０（６），ｃ＝１２．３３８（８），α＝１０９．８１（４），β＝１１７．２０（４），γ＝９０．５１（５）°，Ｖ＝１８４８．８３，Ｍｒ＝２０２０．６，Ｄｃ＝１．８１ｇ／ｃｍ３，Ｚ＝１，Ｆ（０００），μ＝１２．９ｃｍ１（ＭｏＫα）对３７４２个可观测反射点（Ｉ＞３σ（Ｉ））最终一致性因子为Ｒ＝０．０１８，Ｒω＝０．０５４。单晶结构分析表明，簇阴离子中两个［Ｍｏ３Ｏ４］４＋单元通过两个＂桥＂金属Ｖ原子连接成一个奇特的环状结构，Ｍｏ－Ｍｏ平均键长为２．５１９（１），Ｍｏ…Ｖ间平均距离为３．６５４。簇阴离子通过Ｎａ＋连成一个一维长链，Ｎａ原子与氧原子形成一个少见的五配位三角双锥结构，Ｎａ－Ｏ距离仅为２．３１２，Ｎａ－Ｏ间较强的相互作用以及无限长链的晶体结构很好地解释了簇合物（１）的稳定性和不溶性。     

Synthesis and Structure of(NH4)_2 [V2O_4(OCH_2COO)_2]

ＳｙｎｔｈｅｓｉｓａｎｄＳｔｒｕｃｔｕｒｅｏｆ（ＮＨ４）２［Ｖ２Ｏ４（ＯＣＨ２ＣＯＯ）２］ＺＨＯＵＺｈａｏ－ｈｕｉ，ＷＡＮＧＪｉｎｚｈｉ，ＷＡＮＨｕｉ－ｌｉｎａｎｄＴＳＡｌＫｈｉ－ｒｕｉ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＸｉａｍｅｎＵｎｉ...     

CRYSTAL STRUCTURE OF COMPLEX OF ERBIUM(Ⅲ) AND QLYCINE,[Er(GLy)_2(H_2O)_4]_2(ClO_4)_6·4(C_4H_8O_2)

<正> The crystal structure of [Er(Gly)2 (HaO)4]2(ClO4)6.4(Dio) (Gly= NH2CH2COOH; Dio=dioxane) has been determined belonging to triclinic system with space group P1.The final R was 0.055. The carboxyl groups of Gly are associated to Er(Ⅲ) atoms to act as the bidentate bridging ligands.     

Synthesis and Crystal Structure of (C_6N_3H_(18))_2Ti_4O_4(C_2O_4)_7·4H_2O

1 INTRODUCTION The open-framework inorganic materials have been synthesized before the early 1980s[1]. Parti- cularly, metal phosphates have been investigated widely during the past few years[2, 3]. In recent years, considerable efforts have been devote…     

ELECTRONIC ABSORPTION SPECTRA OF Cu(O_4H_4O_5)_2 ·2H_2O CRYSTAL

<正> The electronic absorption spectra of the'crystal of Cu(CtfH505) g-2H20 were measured. The experimental results were discussed quantitatively by using the ligand field theory and the radial wave function of nonfree copper(II). The electronic structure of the compound is in agreement with its crystal structure.     

CRYSTAL STRUCTURE OF [Et_4N]_2[Mo_2O_2(μ-S)_2(S_2)_2]

<正> [(C2H5)4N]2[Mo2o2S2(S2)2], Mr = 676. 74, monoclinic, P21/c, a = 13.510(2), b = 14.373(2), c=14. 777(3)(?), β = 97.53(2)°, V = 2844.7(9) (?)3, Z = 4, Dc= 1. 58g/cm3, μ(MoKα) = 13.0cm-1, F(000) = 1384, R =0. 033 for 1803 observed reflections. The structure contains discrete [Mo2O2S2(S2)2]2- anions and Et4N+ cations. The two oxygen atoms bonded to the Mo atoms are in cis-form with respect to the Mo2S2 bridging unit, with an average Mo- O distance of 1. 678 (?), The Mo…Mo distance is 2. 832(1)(?).     

Synthesis and Crystal Structure of［（n－Bu）_4N］_2［Mo_4O_（10）（OC_（10）H_6O）_2（OCH_3）_2］

ＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ［（ｎ－Ｂｕ）_４Ｎ］_２［Ｍｏ_４Ｏ_（１０）（ＯＣ_（１０）Ｈ_６Ｏ）_２（ＯＣＨ_３）_２］￥ＬｕＸｉａｏ－Ｍｉｎｇ；ＺｈｕＨｕｉ－Ｊｕ；ＹａｎｇＮｉｎｇ；ＬｉｕＳｈｕｎ－Ｃｈｅｎｇ；ＪｉｎＸ?..     

［（n－C_4H_9）_4N］_2［（OC_（14）H_8O）_2Mo_4O_（10）（OCH_3）_2］的合成和晶体结构

为探讨钼多酸根阴离子在有机化学反应中的催化机理，用菲醌作底物合成了［（ｎ－Ｃ_４Ｈ_９）_４Ｎ］_２［（ＯＣ_（１４）Ｈ_８Ｏ）_２Ｍｏ_４Ｏ（１０）（ＯＣＨ_３）_２］配合物。Ｘ射线单晶结构分析表明，该晶体属单斜晶系，空间群Ｐ２_１／ｃ，ａ＝１．３１４９（５）ｎｍ，ｂ＝１．８６６６（８）ｎｍ，ｃ＝１．８９０３（３）ｎｍ，β＝１０４．０６（３）°，Ｚ＝２．收集到独立衍射点３５０５个，其中１３８２个为可观测点，最终一致性因子Ｒ＝０．０７８．结构分析结果表明，菲醌与钼多酸根在不同的实验条件下，能形成配比、氧化态以及结构不同的配合物。     

STRUCTURE OF { CEu_2 (OOCCH_2NHCOCH_2NH_3)_4 (H_2O)_4]·(C1O_4)_6·4H_2O}_n

<正> {[Eu(OOCCH2NHCOCH2NH3)2(H2O)2]·(ClO4)3·2H2O}2,Mr = 1572,P21/n,a=12. 014(4),b=8. 910(5),c=22. 749(5)A ,β=91. 73(3)°,V = 2034 A3,Z=2,Dx=2. 15g·cm-3,λ(MoKa) = 0. 71073A,R=0. 060 for 3107 unique observed reflections (I≥3σ(I)). The complex cation is of one-dimensional chain structure in which the basic unit is a dinuclear complex and the gly-gly ligands are coordinated to metal atoms in two kinds of forms. The overall structure of the dinuclear unit is dioxo and dicarboxyl-bridged.     

THE CRYSTAL AND MOLECULAR STRUCTURE OF (QH)_3[Mo_2O_4(■-COO)(NCS)_4]·H_20 AND (QH)_3[Mo_2O_4(CH_30H)(NCS)_5]

<正> INTRODUCTION. In the reported crystal structures of di(μ-X)(X=O,S)-bridged oxodimolybdates (Ⅴ), the local, symmetric array of donor atoms linked to the Mo atoms is well known. The title compounds (QH)_3[Mo_2O_4(COO)-(NCS)_4]-H_2O(Ⅰ) and (QH)_3[Mo_2O_4(CH_3OH)(NCS)_5](Ⅱ), in which the environments