SYNTHESES AND CRYSTAL STRUCTURES OF (Et_4N)_2(Fe_2Se_2(SPh)_4) AND (Et_4N)_2(Fe_4Se_4Cl_4)

<正> Since the discovery of iron-sulfur proteins , a number of analogous compounds of the active sites of iron-sulfur proteins has been synthesized and characterized . Due to the similarity between sulfur and selenium, some selenoproteins with similar active site as iron-sulfur proteins were found . We have synthesized a series of iron-selenium compounds in correlative study with the iron-sulfur compounds. In this paper, we will discuss the syntheses and crystal stuctures of the title compounds. The spectroscopic properties of these compounds have been under investigation.     

Rh2(CO)4(μ-Cl)2和Rh4(μ-CO)3(CO)4的简正振动分析

金属簇合物具有独特的结构和成键方式。本文对铑簇合物的简正振动分析进行了研究。通过红外光谱用石蜡油糊涂KBr和聚乙烯窗口, 在Nicolet 200SXV FT-IR光谱上测定了Rh2(CO)4(μ-Cl)2的构型, 并使用分子振动全分析程序MVTA(Basic语言), 在PC机上进行计算。     

New 1D and 2D metal oxygen connectivities in Cu(II) succinato and glutarato coordination polymers: [Cu3(H2O)2(OH)2(C4H4O4)2] · 4H2O, [Cu4(H2O)2(OH)4(C4H4O4)2] · 5H2O and [Cu5(OH)6(C5H6O4)2] · 4H2O

Two Cu(II) hydroxo succinates [Cu₃(H₂O)₂(OH)₂(C₄H₄O₄)₂]?·?4H₂O (1) and [Cu₄(H₂O)₂(OH)₄(C₄H₄O₄)₂]?·?5H₂O (2) and one Cu(II) hydroxo glutarate [Cu₅(OH)₆(C₅H₆O₄)₂]?·?4H₂O (3) have been prepared and structurally characterized by single crystal X-ray diffraction methods. They feature 1D and 2D copper oxygen connectivity of elongated {CuO₆} octahedra in “4?+?1?+?1” and “4?+?2” coordination geometries. Within 1, linear trimers of three edge-sharing {CuO₆} octahedra are connected into copper oxygen chains, which are bridged by the anti conformational succinate anions to generate 2D layers with mono terminally coordinating gauche succinate anions on both sides. The layers are assembled into a 3D framework by interlayer hydrogen bonds with lattice H₂O molecules distributed in channels. Different from 1, the principal building units in 2 are linear tetramers of four edge-sharing {CuO₆} octahedra. The tetramers are condensed into copper oxygen chains and the succinate anions interlink them into a 3D framework with triangular channels filled by lattice H₂O molecules. The {CuO₆} octahedra in 3 are edge-shared to form unprecedented 2D inorganic layers with mono terminally coordinating glutarate anions on both sides. Interlayer hydrogen bonding interactions are responsible for supramolecular assembly of the layers into a 3D framework with lattice H₂O molecules in the channels. The inorganic layers in 3 can be described as hexagonal close packing of oxygen atoms with the Cu atoms in the octahedral cavities. The title compounds were further characterized by elemental analyses, IR spectra and thermal analyses.     

Identification of the cobalt(II) chloride ‘mixed’ solvate Co4Cl8(H2O)4(MeCN)6: the ionic structure trans-[Co(H2O)2(MeCN)4] trans-[Co(H2O)2(MeCN)2(CoCl4)2]

The structure of the title compound features mononuclear octahedral Co^II cations, trans-[Co(H₂O)₂(MeCN)₄]²⁺, and trinuclear anions, trans-[Co(H₂O)₂(MeCN)₂(CoCl₄)₂]^2–; the latter centrosymmetric units contain a central octahedral Co(H₂O)₂(MeCN)₂ moiety with two tetrahedral [CoCl₄]^2– ligands. These two large ions are held in a network of intra- and inter-molecular hydrogen bonding.     

[(C_(16)H_(32)N_4)~(-4)·2Mn~(2+)·4HCl·[(C_(16)H_(36)N_4)·2H_2O]多元包合物的晶体结构

[(4氮间杂六甲基十四烷环)~(-4)·2Mn~(2+)]·4HCl·[4氮间杂六甲基十四烷环)·2H_2O]的晶体结构已用单晶X线衍射技术测定完成。它属于三斜晶系,P_1空间群,晶胞参数a=9.028(2),b=11.055(2),c=12.202(4),α=71.70(2),B=88.41(2),γ=75.32(2)~°,Z=1。对于2597个可观察独立反射计算R=0.073。结构分析证实,该晶体存在有四类物种,由负4价的四氮间杂六甲基十四烷环(简称电负性大环Ⅱ),2个Mn~(2+)正离子,4个HCl分子和一个携带2个结晶水的4氮间杂六甲基十四烷环(简称电中性大环Ⅰ)组成。 4个HCl分子处于电负性大环Ⅱ的周围,大环Ⅱ和Mn~(2+)离子间按离子键特点取空间最稳定构型与电中性大环Ⅰ沿c方向周期性交替排布,构成四元包合物O~-、N~-、Cl~-等电负性强的离子之间形成很强的H键网。 六十年代以来,以四氨间杂六甲基十四烷环作配体,以Co~(2+)、Co~(3+)、Ni~(2+)等金属离子为络合中心的大环络合物,国外已有许多报导。这些结构的共同特点是大环配体的4个氮原子围绕金属离子以构成四配位或六配位结构,研究表明,络合以后金属的电子组态发生了变化。 近来,我们将Mn~(2+)与上述的配体反应,结果得到与上述结构绝然不同的化合物。NMR谱证实,该化合物中包含电中性和电负性两种大环。环伏安法测其锰离子是2价正离子(详见     

Vibrational spectroscopic characterization of the phosphate mineral hureaulite – (Mn,Fe)5(PO4)2(HPO4)2·4(H2O)

This research was done on hureaulite samples from the Cigana claim, a lithium bearing pegmatite with triphylite and spodumene. The mine is located in Conselheiro Pena, east of Minas Gerais. Chemical analysis was carried out by Electron Microprobe analysis and indicated a manganese rich phase with partial substitution of iron. The calculated chemical formula of the studied sample is: (Mn_3.23, Fe_1.04, Ca_0.19, Mg_0.13)(PO₄)_2.7(HPO₄)_2.6(OH)_4.78. The Raman spectrum of hureaulite is dominated by an intense sharp band at 959 cm⁻¹ assigned to PO stretching vibrations of HPO₄²⁻ units. The Raman band at 989 cm⁻¹ is assigned to the PO₄³⁻ stretching vibration. Raman bands at 1007, 1024, 1047, and 1083 cm⁻¹ are attributed to both the HOP and PO antisymmetric stretching vibrations of HPO₄²⁻ and PO₄³⁻ units. A set of Raman bands at 531, 543, 564 and 582 cm⁻¹ are assigned to the ν₄ bending modes of the HPO₄²⁻ and PO₄³⁻ units. Raman bands observed at 414, and 455 cm⁻¹ are attributed to the ν₂ HPO₄²⁻ and PO₄³⁻ units. The intense A series of Raman and infrared bands in the OH stretching region are assigned to water stretching vibrations. Based upon the position of these bands hydrogen bond distances are calculated. Hydrogen bond distances are short indicating very strong hydrogen bonding in the hureaulite structure. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral hureaulite to be understood.     

[Ho_2(phen)_4(H_2O)_4(OH)_2](phen)_2(NO_3)_4的合成、晶体结构及磁性

在甲醇与水的混合溶剂中,经浓硝酸硝化的Ho_2O_3与1,10-邻菲啰啉反应形 成氢氧根桥联的双核钬配合物[Ho_2(phen)_4(H_2O)_4(OH)_2] (phen)_2(NO_3)_4 （phen = 1,10-邻菲啰啉）。单晶X射线衍射晶体结构测定表明晶体属三斜晶系, P1-bar (no. 2)空间群,晶胞参数a = 1.1241(1) nm, b = 1.1439(1) nm, c = 1. 4058 (1) nm, α = 93.989(7)°, β = 98.173(7)°, γ = 108.19(1)°, V = 1.6874(4) nm~3, Z = 1, D_c = 1.737 g/cm~3, F(000) = 880,7752个独立衍射 点中,5702个可观测点满足F_o~2 ≥ 2σ (F_o~2),R_1 = 0.0499, wR_2 = 0. 858。标题配合物由中心对称的双核[Ho_2(phen)_4(H_2O)_4-(OH)_2]~(4+)配阳离 子,邻菲啰啉phen分子及硝酸根NO_3~-阴离子组成。敏个稀土原子与2个邻菲啰啉 配体,2相水分子和2个氢氧根配位形成配位数为8的[HoN_4O_4]四方反棱柱。配位 多面体通过两氢氧根基团形成共棱的[Ho_2N_8O_6]双四方反棱柱[d(Ho-N) = 0. 2549～0.2565 nm, d(Ho-O_(H_2O) = 0.2356, 0.2366 nm, d(Ho-O_(OH)) = 0. 2223, 0.2240 nm]。通过氢键和芳环堆积作用,配阳离子和邻菲啰啉分子排列形成 平行于（10 1-bar）的两维层结构,NO_3~-阴离子位于层之间。标题配合物为顺磁 物质,在5 ～300K区间内遵循Curie-Weiss定律X_m (T + 4.43) = 14.72 cm~3·K ·mol~(-1)(X_m为每摩尔Ho~(3+)离子磁化率）,其Ho~(3+)离子的室温有效磁矩为 10.76 B. M.,与Ho~(3+)自由离子的磁矩基本相同,表明稀土离子间不存在磁交换 作用。     

SINGLE Mo_(n)Fe_(4-n)S_(4) (n=0, 1, 2) CUBANE-LIKE CLUSTERS: PREPARATION FROM COMBI-NATION OF DINUCLEAR COMPLEXES AND THE STRUCTUREOF [Mo_(2)Fe_(2)S_(4)(C_(4)H_(8)dtc)_(6)]·3.5C_(2)H_(2)Cl_(4)

Three types of unit combinations, FeS2Fe + FeS2Fe, FeS2Fe + MoS2Fe and MoS2Mo + MoS2Mo, lead to Fe4S4, MoFe3S4 and Mo2Fe2S4 cubane-like clusters, respectively. A new doubly bridged single cubane cluster [Mo2Fe2S4(C4H8dtc)6]·3.5C2H2Cl4 has been obtained and its structure is discussed.     

Synthesis and structure of (NH4)2[(UO2)2(C2O4)(CH3COO)4] · 2H2O

Single crystals of (NH₄)₂[(UO₂)₂C₂O₄(CH₃COO)₄] · 2H₂O have been synthesized and studied. The compound crystallizes in the orthorhombic system with the unit cell parameters a = 6.9225(14) Å, b = 12.327(3) Å, c = 14.619(3) Å, space group Immm, Z = 2, and V = 1247.6(5) ų. The main structural units of the crystals are the isle binuclear groups [(UO₂)₂C₂O₄(CH₃COO)₄]^2? belonging to the crystal-chemical group A₂K⁰²B ₄ ⁰¹ (A = UO ₂ ²⁺ , K⁰² = C₂O ₄ ^2? , B⁰¹ = CH₃COO^?) of the uranyl complexes. The uranium-containing groups are linked into a three-dimensional framework due to electrostatic interaction with the ammonium cations and through a system of hydrogen bonds involving atoms of the water molecules, oxalate and acetate ions, and ammonium and uranyl cations.     

由己二酸根桥联的新颖双U形四核铜配合物:[Cu4(phen)4(NO3)2(H2O)2(adip)4/4(Hadip)4/2](NO3)2·2H2O

邻菲罗啉、己二酸和硝酸铜在水溶液中反应得到一种新颖的四核铜配合物[Cu4(phen)4(NO3)2(H2O)2-(adip)4/4(Hadip)4/2](NO3)2·2H2O(其中H2adip=己二酸),并经元素分析,IR,UV,TG和X射线单晶衍射分析表征.该配合物晶体属三斜晶系,P-1空间群,a=1.0146(2)nm,6=1.0261(2)nm,c=1.8285(4)nm,a=91.66(3)°,β=92.19(3)°,γ=112.76(3)°,V=1.7520(6)nm3,Z=1,Dc=1.639 g/cm3,c66H66Cu4N12O28,Mr=1729.47,F(000)=886,μ=1.294mm-1,R1和wR2分别为0.0447和0.1141.己二酸根通过4个羧基O将两个U形双核亚单元联接成具有一个对称中心的双U形四核结构,其中每个U型亚单元包含晶体学上不对称的2个Cu(Ⅱ)原子.每个Cu(Ⅱ)离子均处于畸变的四方锥配位环境,除与己二酸氢根(Hadip)、己二酸根(adip)和邻菲罗啉(Phen)的N,O配位形成锥底平面外,其中的1个Cu(Ⅱ)与水配位,而另一个Cu(Ⅱ)则与硝酸根配位.配合物晶体结构中存在着广泛的氢键和π…π作用.     

Synthesis, molecular structures, and properties of heterometallic cobalt tetramethylcyclobutadiene complexes (C4Me4)Co(CO)2TePh, (C4Me4)Co(CO)2TePh[W(CO)5], and Me4C4Co(μ3-S)2Cr2Cp2(μ-SC4H9)

The reaction of Cb*Co(CO)₂I (1) (Cb* is tetramethylcyclobutadiene) with sodium phenyltelluride afforded the mononuclesar complex Cb*Co(CO)₂TePh (2). The reaction of the latter with W(CO)₅(THF) produced the Cb*Co(CO)₂TePh[W(CO)₅] compound (4). The reaction of 1 with the Cp₂Cr₂(SCMe₃)₂S complex gave the heterometallic cluster Cb*Co(μ₃-S)₂Cr₂Cp2 (μ-SCMe₃) (5). Complexes 2, 4, and 5 are diamagnetic. Their structures were determined by X-ray diffraction. Complex 2 contains the Co-Te bond (2.585(1) Å); complex 4, the Co-Te (2.558(8) Å) and W-Te (2.8467(6) Å) bonds. Complex 5 has the stable triangular sulfide-and tert-butylmercaptide-bridged core Cr₂Co (Cr-Cr and Cr-Co bond lengths are 2.626(2) and 2.673(2) Å, respectively) with Cp ligands at the chromium atoms and a Cb* ligand at the cobalt atom. Complex 5 was characterized by cyclic voltammetry. The thermolysis of complex 4 was studied.     

Synthesis and X-ray diffraction study of K4[(UO2)2(C2O4)3(NCS)2] · 4H2O

Single crystals of K₄[(UO₂)₂(C₂O₄)₃(NCS)₂] · 4H₂O(I) have been synthesized and studied by X-ray diffraction. The crystals are monoclinic with the unit cell parameters a = 8.0226(7) Å, b = 14.9493(11) Å, c = 11.1670(9) Å, β = 98.299(3)°, space group P2₁/n, Z = 2, V = 1325.26(19) ų, R = 0.0186. The main structural units of the crystals of structure I are discrete binuclear groups [(UO₂)₂(C₂O₄)₃(NCS)₂]^4? belonging to the crystal-chemical group A₂K⁰²B ₂ ⁰¹ M ₂ ¹ (A =UO ₂ ²⁺ , K⁰² =C₂O ₄ ^2? , B⁰¹ =C₂O ₄ ^2? , M¹ = NCS^?) of the uranyl complexes. The uranium-containing complexes are linked into a three-dimensional framework through the potassium ions and a system of hydrogen bonds involving the outer-sphere water molecules.     

SYNTHESIS AND STRUCTURE OF (Et_4N) [Fe_4S_4 (Et_2NCS_2)_4 ]

<正> INTRODUCTION. The Fe_4S_4 cubane-like clusters have been extensively studied as the model compounds for the active center of the Fe-S proteins in the last fifteen years. Coucouvains et al. have recently reported the syntheses and structures of a few Fe_4S_4 cluster compounds containing R_2NCS_2(R_2dtc) and RS (or Cl) mixed terminal ligands and having [Fe_4S_4]~(2+) core oxi-     

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.     

(NH4)2SO4-NH4SCN-RhB-H2O体系浮选分离汞(Ⅱ)的研究

[Hg(SCN)4]^2-与罗丹明B阳离子(RhB^ )形成不溶于水的三元配合物(RhB)2[Hg(SCN)4]，在一定量(NH4)2SO4存在下，此三元配合物可浮于盐水相上形成界面清晰的两相，在两相形成过程中，Hg^2 被定量浮选，而Cd^2 、Cu^2 、Mn^2 、CO^2 、Ni^2 、Ee^2 、Al^3 等不被浮选，无需加入掩蔽剂就可实现Hg^2 与这些离子之间的定量分离。与其它体系相比，该体系无毒、无环境污染、分相速度快、相分离界面清晰、操作简便、成本低。     

CRYSTAL STRUCTURE OF Mo_2(u-S)_2(S_2P(OEt)_2)_4

<正> Mr=996.91, triclinic, P1, a=8.773(2), b=9.712(3), c=13.652(1) A; α=69.24(0), β=70.43(3), γ=66.87(l)°; Z=l, Dx=1.699 g/cm 3. Final R=0.053 for 3186 reflections with I≥3a(I). There is an interesting trans influence of μ-s bridge in this binuclear cluster. Mo-Mo distance is 2.752(1) A.     

三核簇合物(Et_4N)_2[(CO)_4MoS_2MoS_2Mo(CO)_4]和(Et_4N)_2[(CO)_4MoS_2WS_2Mo(CO)_4]的合成及晶体结构

合成了含Mo(O)的三核化合物(Et_4N)_2.[(CO)_4Mo(μ-S)_2Mo(μ-S)_2Mo(CO)_4](Ⅰ)和(Et_4N)_2[(CO)_4Mo(μ-S)_2W(μ-S)_2Mo(CO)_4](Ⅱ),测定了(Ⅰ)的晶体结构.Ⅰ属单斜晶系,空间群P2_1/c,a=22.790(5),b=8.701(1),c=17.764(5)(?).γ=94.09(2)°,Z=4,最终R=0.045.Ⅰ的阴离子中,三个Mo间键角175°,接近共线.整个阴离子可以看作是由2个以Mo(0)为中心的八面体和1个以Mo(Ⅵ)为中心的准四面体分别共用一条边(各由2个μ-S原子连线所成)组成的结构.Mo-Mo-Mo键距分别是2.998(1)和3.000(1),Mo(μ-S)_2Mo共平面.