Syntheses and characterizations of cluster compounds with MoFe3Se4 cubane-like core

The reaction system of [Et4N]2MoSe4, FeCI2 and R2NCS2Na in DMF-CH3CN at ambient temperature yielded the Mo-Fe-Se cluster compounds MoFe3Se4(μ-R2NCS2)2(R2NCS2)4 (R2=Me2(1), Et2(2), C4H8(3)) with MoFe3Se4 core. X-ray diffraction analyses of 2 revealed that the molecular structure contains a distorted cubane like M4Se4 core with two bridged and four chelated Et2NCS2- ligands. The cyclic voltammetric studies of the compounds showed the reversible mul-tielectron-transfer sequence.     

Syntheses and structural characterizations of Fe_4S_4 cubane-like cluster compounds containing cycloalkylthiolate ligands

In a reaction system consisting of FeCl2,tetrathiometallate and cycloalkylthiolate,two Fe4S4 cubane-like cluster compounds were obtained with the following crystallographic data:(PhCH2NMe32[Fe4S4 (SC5H9)4](Ⅰ),monoclinic space group P21/c,a=1.6327(4),6=1.1229(3),c=2.802 5( 10) nm,β=94.63(2)°,Z=4,and R=0.074; (Et4N)2[Fe4S4(SC6H11)4](Ⅱ),tetragonal space group I42m,a=1.16705(9),b=1.167 06(2),c=2.063 26(5) nm,Z=2,Dabs=1.28 g/cm3,and R=0.078 The participation of cy-cloalkylthiolate ligand does not obviously arouse the change of the Fe4S4 core structure.Meanwhile,the influence of the cation on the structural symmetry of the Fe4S4 cluster dianion is also discussed.     

Syntheses and structural characterizations of Fe4S4 cubane-like cluster compounds containing cycloalkylthiolate ligands

In a reaction system consisting of FeCl₂, tetrathiometallate and cycloalkylthiolate, two Fe₄S₄ cubanelike cluster compounds were obtained with the following crystallographic data: (PhCH₂NMe₃)₂ [ Fe₄S₄ (SC₅H₉)₄] (I), monoclinic space groupP2₁/c,a = 1.632 7(4),b=1.122 9(3),c = 2. 802 5(10) nm, β= 94.63(2)°, Z=4, andR= 0.074; (Et₄N)₂[F₄S4(SC₆H_lI)₄] (II), tetragod space group ,a = l.167 05(9),b = 1.167 06(2),c = 2.063 26(5) nm,Z = 2, D_obs = 1. 28 g/cm³, andR = 0. 078. The participation of cycloalkylthiolate ligand does not obviously arouse the change of the Fe₄S₄ core structure. Meanwhile, the influence of the cation on the structural symmetry of the Fe₄S₄ cluster dianion is also discussed. Project supported by the National Natural Science Foundation of China and the Climbing Program Foundation of China.     

Synthesis and structure of a novel MoFe4S4 cubane-like cluster (Me3PhCH2N)2 [MoFe4S4 (SC6H11)7]

A novel (Me₃PhCH₂N)₂[MoFe₄S₄(SC₆H₁₁)₇] cubane-like cluster was obtained from a reaction system including (NH₄)₂MoS₄, FeCl₂ and NaSC₆H₁₁ in methanol, and characterized by X-ray crystallography. The title compound crystallizes in triclinic space group witha = 1.523 1(3), b =1.610 5(3),c = 1.838 3(4) nm, α = 77.18 (3)°, β = 75.17(3)°, γ = 64.60(3)°, and Z = 2. Also included in this paper are the discussions on the variation of the reaction products obtained from the participation of cyclohexylthiolate and on the changes of the structural features of the products. Project supported by the National Natural Science Foundation of China and the Climbing Program—State Key Project for Fundamental Research in China, and Hong Kong Research Grants Council (Earmarked Grant No. CUHK. 311/94p).     

Synthesis and structure of a novel MoFe_4S_4 cubane-like cluster (Me_3PhCH_2N)_2[MoFe_4S_4(SC_6H_(11))_7]

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Synthesis and structure of cluster compounds containing a novel cluster core {Re4STe3}

Three novel cluster compounds K₄[Re₄STe₃(CN)₁₂]·₄H₂O (I), [{Cu(en)₂}₂Re₄STe₃(CN)₁₂]·₅H₂O (II) and [{Cu(trien)}₂Re₄STe₃(CN)₁₂]·2H₂O (III) (en is ethylenediamine, trien is triethylenetetraamine) containing a new cluster core {Re₄STe₃} have been prepared and structurally characterized. According to single crystal X-ray diffraction data, compound I is ionic and represents the arrangement of ions K⁺ and [Re₄STe₃(CN)₁₂]^4?; compounds II and III are molecular and formed by two cationic moieties {Cu(en)₂}²⁺ and {Cu(trien)}²⁺, respectively, coordinated to one cluster anion. In the solid state, S atom positions in the tetrahedron Q₄ (Q = S, Te) are disordered for all three compounds: in I and III sulfur atoms are split over all four Q positions, while in II over two positions.     

一个多酸簇合物[Cu4(PPh3)6][Mo8O26]的合成、晶体结构和非线性光学性质

本文报道了一个多酸簇合物[Cu4(PPh3)6][Mo8O26]的合成、X-射线单晶结构分析及IR、XRD表征.单品结构表明中心对称的[Mo8O26]4-是由8个共边的MoO6八面体组成.该化合物具有较好的三阶非线性光学性质,其三阶非线性吸收和折射系数分别为12.9×10-11 MKS和3.13×10-11 esu.     

Syntheses,crystal structures,and characterizations of two novel cubane-like and double cubane-like molybdenum-copper-sulphur clusters {MoCu3S3(S2COEt)}(O)(Ph3P)3 and {Mo2Cu6S6(SCMe3)2}(O)2(Ph3P)4

Two novel heterometallic cubane-like and double cubane-like clusters, {MoCu₃S₃(S₂COEt)}(O)(Ph₃P)₃ I and {Mo₂Cu₆S₆(SCMe₃)₂}(O)₂(Ph₃P)₄ II, were synthesized by reaction of {MoCu₂S₃}(O)(Ph₃P)₃ with CuS₂COEt and CuSCMe₃, respectively. ClusterI crystallized in the triclinic space group (2) witha=12.766(6) Å,b=22.904(5) Å,c=10.522(3) Å, =99.86(2)°, =109.68(2)°, =86.84(3)°,V=2854(2) ų,Z=2,R=0.049 for 6622 observed reflections (I>5(I)) and 410 variables. ClusterII crystallized in the triclinic space group (2) with dimensionsa=14.212(4) Å,b=14.725(5) Å,c=12.396(8) Å, =110.32(4)°, =90.40(5)°, =62.88(2)°,V=2129(2) ų,Z=1,R=0.039 for 6020 observed reflections (I>3(I)) and 461 variables. ClusterI consists of a neutral cubane-like molecule with the core {MoCu₃S₃(S₂COEt)}²⁺, in which one corner of the cubane-like core is a novel triply bridging bidentate 1,1-dithiolato (xanthate, S₂COEt^–) ligand. ClusterII is a double cubane-like one, in which two cubane-like cores {MoCu₃S₃(SCMe₃)}²⁺ are connected by two Cu-S bonds of the triply bridging monothiolato (SCMe ₃ ^– ) ligand. Two different pathways of unit construction from a small heterometallic cluster {MoCu₂S₃}(O)(Ph₃P)₃ have been outlined. Comparisons of the selected bond lengths and bond angles for the cubane-like core {MoCu₃S₃ X} (X=Cl^–, Br^–, S₂COEt^–, SCMe ₃ ^– ) are given. Spectroscopic properties of the title clusters are also reported.     

四核钴羰基簇合物Co4(CO)8(μ-CO)2(μ4-PSR)2的合成和晶体结构

The title compounds Co4(CO)8(μ-CO)2 (μ4-PSR) [R=-CH3, -C2H5, -C(CH3)3,-(CHa)4CH3] were synthesized by the reaction of Co2(CO)8 with RSPCl2. They were characterized by IR, 1HNMR, elemental analysis. The crystal and molecular structure of Co4(Co)8(μ-CO)2 (μ4-PSC2H5) has been determined by single crystal diffraction method. Crystal data: monoclinic, space group P21 /c, with a=8-445(3), 6=8.562(3), c= 17.125(6)Å, β=104.26 (3)' 9 V=1200.1Å3, Z=2, Dc=1.937gcm-3. Its molecular structure contains an octahedral Co4P2 skeleton which consists of a rectangular four cobalt atoms core and the Co4 core is capped above and below by two quadruply bridging PSR ligands.     

金属硫族化合物CsSb2(Se2)0.5Se3的溶剂热合成及其晶体结构分析

以有机溶剂热生长技术(Solvothermal Technique)在180 ℃乙二胺(en)溶液中以SbCl₃与碱金属硒化物Cs₂Se和Se在密闭容器中反应7 d,制备出新的金属硫族化合物CsSb₂(Se₂)_0.5Se₃。以单晶X射线衍射技术测得晶体结构属三斜晶系,空间群为P1,晶胞参数：a=0.653 0(2) nm,b=0.707 1(3) nm,c=0.979 9(4) nm,α=80.37(3)°,β=86.28(3)°,γ=74.61(3)°,V=0.430 0(3) nm³,Z=2。     

Crystal and electronic structure of the red semiconductor Ba4LaSbGe3Se13 comprising the complex anion [Ge2Se7-Sb2Se4-Ge2Se7]

Ba₄LaGe₃SbSe₁₃ was prepared by reacting the elements under exclusion of air at 700°C, followed by slow cooling to room temperature. It crystallizes in a new type of the monoclinic space group P2₁/c, with lattice dimensions of a=1633.30(9) pm, b=1251.15(7) pm, c=1303.21(7) pm, β=103.457(2)°, V=2590.0(2) 10⁶ pm³ (Z=4). The structure contains isolated GeSe₄ as well as Ge₂Se₇ digermanate units. Two of the latter are interconnected via an Sb₂Se₄ bridge yielding an almost linear complex anion [Ge₂Se₇-Sb₂Se₄-Ge₂Se₇]¹⁴⁻. The oxidation states are assigned to be Ba^II, La^III, Ge^IV, Sb^III, and Se^−II, in accord with an electronically saturated nonmetal. The lone pair of Sb^III reflects itself in highly irregular Se coordination. The red color of the material is indicative of semiconducting behavior with an activation energy of 2.0 eV. Electronic structure calculations based on the LMTO approximation point to a smaller gap, typical for this calculation method. We utilized the COHP tool to explore the bonding character of the different Sb-Se interactions.     

镉汞四元硒化物K8Cd2.79Hg9.21Se16和Rb4Hg3.04Cd2.96Se8的溶剂热合成及表征

利用溶剂热法合成了2种含镉汞的二维(2D)四元硒化物K8Cd2.79Hg9.21Se16(1)和Rb4Hg3.04Cd2.96Se8 (2)。单晶X射线衍射分析表明,化合物1为正交晶系,空间群为Pbcn,a=1.082 71(17) nm,b=0.678 73(10) nm,c=1.415 0(2) nm,Z=1;化合物2为正交晶系,空间群为Ibam,a=0.640 72(10) nm,b=1.160 25(16) nm,c=1.452 0(2) nm,Z=2。化合物1中含有八元环Cd2Hg2Se4和六元环CdHg2Se3阴离子层(Cd2.79Hg9.21Se16)n8n-;化合物2中含有八元环Cd2(Cd/Hg)2Se4及四元环CdHgSe2和(Cd/Hg)2Se2阴离子层(Hg3.04Cd2.96Se8)n4n-。对这2种化合物进行了扫描电镜和能谱分析、粉末X射线衍射、差示扫描量热分析、固体-可见漫反射光谱和荧光性质等表征。     

铁氧簇合物[Fe11O6(OH)6(O2CCH3)15](C5H5N)6的结构和磁性质

通过三核铁盐[Fe₃O(O₂CCH₃)₆(H₂O)₃]C1在吡啶溶液中水解聚合得到铁氧簇合物[Fe₁₁O₆(OH)₆(O₂CCH₃)₁₅](C₅H₅N)₆。晶体结构表明11个铁离子(Ⅲ)中6个位于扭曲的三棱柱的顶点上，其余5个分别位于三棱柱的每个面之外。铁离子(Ⅲ)之间以氧桥或者羟基氧桥相连。变温磁化率证实铁离子(Ⅲ)之间是反铁磁耦合的。     

Unusual Disordering of Potassium Ions in the Structures of Cluster Rhenium Thiohalides K3[Re6S7Br7] and K4[Re6S8Cl6]

New cluster compounds — rhenium and potassium thiohalides K₃Re₆S₇Br₇ (I) and K₄Re₆S₈Cl₆ (II) — have been synthesized. Their crystal structures have been determined by single crystal X-ray diffraction. The compounds are monoclinic; (I): space group P2₁/c, a = 9.32(1) Å, b = 13.528 Å, c = 12.413 Å, β = 110.21°, Z = 2, R = 0.038; (II): space group C2/m, a = 10.614 Å, b = 17.268 Å, c = 10.448 Å, β = 110.755°, Z = 2, R = 0.042. In both structures, the potassium ions are considerably distorted. The occupancies of the potassium sites are 0.17-0.34 (I) and 0. 01-0.26 (II), correlating well with the coordination numbers (c.n. 7-10 and 2-7 for I and II, respectively). In I, adjacent positions of potassium atoms are aggregated into discrete tetrahedral and angular clusters; in II, the individual (four-and six-membered) cyclic clusters of potassium sites are present along with bent chains of vertex-and edge-sharing tetrahedral “potassium clusters.” The shortest K-K distances in these “clusters” vary from 1.31 Å to 1.54 Å (I) and from 0.66 Å to 1.65 Å (II). The “instability” of the potassium site suggests that I and II are ion conductors.Original Russian Text Copyright © 2004 by S. F. Solodovnikov, S. S. Yarovoi, Yu. V. Mironov, A. V. Virovets, and V. E. Fedorov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 909–917, September–October, 2004.     

Crystal structure and characterization of the bis(n-benzyl-benzotriazole-n3)-dichloro Co(II) complex: CoCl2(C6H4N3CH2Ph)2

The structure of [CoCl₂(C₆H₄N₃CH₂Ph)₂] has been determined by X-ray crystallography. It is also characterized by elemental analysis, IR and electronic spectroscopy, and by thermogravimetric differential thermal analysis. It crystallizes in the monoclinic system, space group C2/c, with lattice parameters a = 16.133(3) , b = 11.355(2) , c = 15.637(3) , = 117.22(3)°, and Z = 8. The crystal structure of the title compound consists of monomeric molecules of [CoCl₂(C₆H₄N₃CH₂Ph)₂] with slightly distorted tetrahedron geometry for the CoCl₂N₂ chromophore. The thermal gravimetry (TG) data indicate that there are four decomposition steps with five endothermic peaks. The final product of the thermal decomposition is CoCl₂. Elemental analysis and the electronic and IR spectra are in agreement with the structural data.Original Russian Text Copyright © 2004 by F. Jian, H. Wang, and H. XiaoTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 723–728, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Synthesis and structural characterization of a new trimetallic thiocubane cluster

The trimetallic cluster W2CuAgS4(TDT)2(PPh3)2-CH2Cl2 (TDT= [S2(C6H3)CH3]2-) (2) has been prepared from the reaction of the well-defined molecule building block [W2S4(TDT)2]2-(1) with AgNO3,CuBr and PPh3.The structure contains a [W2CuAgS4]4+ distorted cubane-like core.Two types of metal-metal bonds exist in the core.One is W-W bond of which length is 0.2871(1) nm,the other is W-M' (M'=Cu or Ag) bonds,whose mean distance is 0.2980 nm.The details of synthesis,structure,IR,UV-Vis and 31P NMR spectra are reported.The crystallographic data are:space group F21/n,with 0=1.6987(4),6=1.7763(6),c=1.8918(5) nm,β=98.54(2)°,V=5.645(3) nm3,Z=4,and final R=0.043 for 6437 observed reflections.     

链状Cs_8Mn_4Sn_4Se_(16)和[Ni(1,2-dap)_3]_2Cd_2Sn_2S_8(1,2-dap:1,2-丙二胺)的溶剂热合成与表征

采用溶剂热法,在1,4-丁二胺中合成以碱金属为客体阳离子的硫属锡酸盐Cs_8Mn_4Sn_4Se_(16)(1)及1,2-丙二胺(1,2-dap)配位的过渡金属为客体阳离子的硫属锡酸盐[Ni(1,2-dap)_3]_2Cd_2Sn_2S_8(2)。并采用单晶X射线、紫外可见漫反射、热重分析-差示扫描量热分析(TG-DSC)等手段进行表征。结果表明,化合物1为正交晶系,空间群为Fddd;化合物2为正交晶系,空间群为Cmcm;且结构中均包含Sn Q4(Q=S,Se)四面体与TMQ_4(TM=Mn,Cd)四面体通过共边而成的一维(1-D)阴离子链,紫外可见漫反射分析表明,化合物1、2的禁带宽度分别为1.70和2.21 e V,具有半导体性质。且TG-DSC测试显示化合物1、2在一定温度下具有一定的稳定性。     

Synthesis and crystal structure of the double cluster [Cp3Fe4(CO)4(C5H4)]2(p-C6H4)

[Cp₄Fe₄(CO)₄] (1) reacts with p-BrC₆H₄Li and MeOH in sequence to afford the functionalized cluster [Cp₃Fe₄(CO)₄(C₅H₄-p-C₆H₄Br)] (2), while the reaction of 2 with n-BuLi and MeOH produces [Cp₂Fe₄(CO)₄(C₅H₄Bu)(C₅H₄-p-C₆H₄Br)] (3). The double cluster [Cp₃Fe₄(CO)₄(C₅H₄)]₂(p-C₆H₄) (4) has been prepared by treatment of [Cp₄Fe₄(CO)₄] with p-C₆H₄Li₂ and MeOH in sequence. The electrochemistry of 2 and 4, as well as the crystal structure of 4 have been investigated.     

Syntheses, crystal structures and characterizations of BaZn(SeO3)2 and BaZn(TeO3)Cl2

Two new barium zinc selenite and tellurite, namely, BaZn(SeO₃)₂ and BaZn(TeO₃)Cl₂, have been synthesized by the solid state reaction. The structure of BaZn(SeO₃)₂ features double chains of [Zn(SeO₃)₂]²⁻ anions composed of four- and eight-member rings which are alternatively along a-axis. The double chains of [Zn₂(TeO₃)₂Cl₃]³⁻ anions in BaZn(TeO₃)Cl₂ are formed by Zn₃Te₃ rings in which each tellurite group connects with three ZnO₃Cl tetrahedra. BaZn(SeO₃)₂ and BaZn(TeO₃)Cl₂ are wide bandgap semiconductors based on optical diffuse reflectance spectrum measurements.     

New Gallium Phosphate Frameworks Containing 1,4-Diaminobutane and 1,5-Diaminopentane: [NH3(CH2)xNH3][Ga4(PO4)4(HPO4)] and [NH3(CH2)xNH3][Ga(PO4)(HPO4)] (x=4 and 5)

Two new gallium phosphates, [NH₃(CH₂)₄NH₃][Ga₄(PO₄)₄ (HPO₄)] (I) and [NH₃(CH₂)₄NH₃][Ga(PO₄)(HPO₄)] (II), have been synthesized under solvothermal conditions in the presence of 1,4-diaminobutane and their structures determined using room-temperature single-crystal X-ray diffraction data. Compound (I) (M_r=844.90, triclinic, space group P-1, a=9.3619(3), b=10.1158(3) and c=12.6456(5) Å, α=98.485(1), β=107.018(2) and γ=105.424(1)°; V=1070.39 ų, Z=2, R=3.68% and R_w=4.40% for 2918 observed data [I>3(σ(I))]) consists of GaO₄ and PO₄ tetrahedra and GaO₅ trigonal bipyramids linked to generate an open three-dimensional framework containing 4-, 6-, 8-, and 12-membered rings of alternating Ga- and P-based polyhedra. 1,4-Diaminobutane dications are located in channels bounded by the 12-membered rings in the two-dimensional pore network and are held to the framework by hydrogen bonding. Compound (II) (M_r=350.84, monoclinic, space group P2₁/c, a=4.8922(1), b=18.3638(6) and c=13.7468(5) Å, β=94.581(1)°; V=1227.76 ų, Z=4, R=2.95% and R_w=3.37% for 2050 observed data [I>3(σ(I))]) contains chains of edge-sharing 4-membered rings of alternating GaO₄ and PO₄ tetrahedra constituting a backbone from which hang ‘pendant’ PO₃(OH) groups. Hydrogen bonding between the GaPO framework and the diamine dications holds the structure together. A previously reported phase, [NH₃(CH₂)₄NH₃][Ga₄(PO₄)₄(HPO₄)] (V), structurally related but distinct from its stoichiometric equivalent, (I), has been prepared as a pure phase by this method. Two further materials, [NH₃(CH₂)₅NH₃][Ga₄(PO₄)₄(HPO₄)] (III) (tricli- nic, lattice parameters from PXD: a=9.3565(4), b=5.0156(2) and c=12.7065(4) Å, α=96.612(3), β=102.747(4) and γ=105.277(3)°) and [NH₃(CH₂)₅NH₃][Ga(PO₄)(HPO₄)] (IV) (M_r=364.86, monoclinic, space group P2₁/n, a=4.9239(2), b=13.2843(4) and c=19.5339(7) Å, β=96.858(1)°; V=1268.58 ų, Z=4, R=3.74% and R_w=4.44% for 2224 observed room-temperature data [I>3(σ(I))]), were also prepared under similar conditions in the presence of 1,5-diaminopentane. (III) and (IV) are structurally related to, yet distinct from (I) and (II) respectively.