锡(Ⅳ)N,N-二取代荒酸配合物Ph3SnS2CN(CH3)C6H5、 Ph3SnS2CN(C4H8NH)和SnCl2(S2CNEt2)2的合成、表征及晶体结构

Three tin (Ⅳ) complexes with N,N-dialkyl dithiocarbamates Ph₃SnS₂CN(CH₃)C₆H₅ (1),Ph₃SnS₂CN(C₄H₈NH) (2) and Sn(Cl)₂(S₂CNEt₂)₂ (3) have been synthesized. The crystal structures have been determined by X-ray sin- gle crystal diffraction. A crystal of the complex 1 is triclinic with space group P1, a=0.9485(3)nm, b=1.0491(3)nm, c=1.3631(4)nm, α=70.996(4)°, β=72.294(4)°, γ=79.609(4)°, Z=2, V=1.2168(6)nm³, D_c=1.453g·cm^-3, μ=1.234mm^-1, R=0.0442, wR=0.0858. A crystal of the complex 2 is monoclinic with space group P2(1)/c, a=1.2214(2)nm, b=1.1651(2)nm, c=1.5769(3)nm,β=99.039(2)°, Z=2, V=2.2162(7)nm³, D_c=1.532g·cm^-3, μ=1.352mm^-1, R=0.0267, wR=0.0591. A crystal of the complex 3 is triclinic with space group P1, a=0.7179(2)nm, b=0.9256(3)nm, c=1.5327(5)nm,α=93.857(4)°,β=98.992(4)°, γ=109.481(4)°, Z=2, V=0.9405(5)nm³, D_c=1.717g·cm^-3, μ=2.076mm^-1, R=0.0263, wR=0.0662. In the complexes 1 and 2 the tin atoms rendered five-coordination in a distorted tigonal bipyramidal structure and in the complex 3 the tin atom rendered six-coordination in a distorted octahedron structure. CCDC: 1, 179918; 2, 180024; 3, 180004.     

[Pb2(TNR)(NO3)2(H2O)]的制备和晶体结构研究

[Pb₂(TNR)(NO₃)₂(H₂O)] was prepared by reaction of the aqueous solution of lead nitrate and magnesium styphnate. The crystal structure of Pb₂(TNR)(NO₃)₂(H₂O)was determined by single crystal diffraction analysis. The crystal is triclinic, space group P1 with crystal parameters a=0.7279(2)nm,b=1.0698(2)nm,c=1.0738(2)nm;α=86.82(1)°,β=89.52(2)°,γ=83.50(2)°;V=0.8295(3)nm³,Z=2,D_c=3.201g·cm^-3, F(000)=716. The final R value is 0.0358.In the crystal structure, one lead ion was represented by nine coor-dination geometry; the other was showed as ten coordination geometry.     

甲酸桥联四核锰配合物[Mn4(O2CH)4(phen)8](ClO4)4·6H2O的水热合成和晶体结构

The title compound, [Mn₄(O₂CH)₄(phen)₈](ClO₄)₄·6H₂O(1), where phen=1,10-phenanthroline, was synthes-ized and its crystal structure was determined by X-ray diffraction structure analysis. The crystal is of monoclinic, space group P2/c with a=1.928 0(16) nm, b=1.297 0(11) nm, c=2.126 4(18) nm, V=5.242 2(8) nm³, Z=2, M_r=2 347.36, D_c=1.487 g·cm^-3, μ=0.659 mm^-1, F(000)=2 400, R_int=0.043 7, R=0.052 3, wR=0.118 6. The Mn atoms are octahed-rally coordinated by two O atoms of two ligands and four N atoms of two 1,10-phenanthroline molecules. The carboxyl group coordinates to Mn(Ⅱ) in the bridging bidentate mode. CCDC: 675520.     

(NH2CH2CH2NH3)4[WⅤO2(OC6H4O)2]2(NH3CH2CH2NH3)·H2O的合成、晶体结构、EPR以及与同构物的比较

Cis-dioxo-catecholatotungsten(Ⅴ) complex (NH₂CH₂CH₂NH₃)₄[W^ⅤO₂(OC₆H₄O)₂]₂(NH₃CH₂CH₂NH₃)·H₂O (1) was synthesized at room temperature by the reaction of tetrabutyl ammonium decatungstate with catechol in the mixed solvent of CH₃OH, CH₃CN and NH₂CH₂CH₂NH₂. The crystal structure of complex was determined by X-ray diffraction structural analysis. The results show that complex belongs to monoclinic system with space group P2₁/c,a=0.712 8(3) nm, b=3.082 3(11) nm, c=0.982 8(4) nm, β=102.639(6)°, V=2.106 8(14) nm³, Z=2, R₁=0.062 8, wR₂=0.183 7. Compared the complex with its analogous complexes (NH₂CH₂CH₂NH₃)₃[Mo^ⅤO₂(OC₆H₄O)₂], it is found that the coordination structure of W have no changes in the processing of electron transfer of tungsten-containing enzymes from the result of the similarity of the EPR spectra of the complexes and flavoenzyme from milk. CCDC: 272937.     

双核配合物[Cu2(L-Asp)(phen)3(NO3)](NO3)·4H2O的合成及晶体结构

The new complex [Cu₂(L-Asp)(phen)₃(NO₃)](NO₃)·4H₂O (L-Asp=L-aspartic acid and phen=1,10-phenanthroline) has been synthesized and its crystal structure has been determined. The complex crystallizes in the monoclinic with space group P2₁/c, The cell parameters are: a=1.261 3(2) nm, b=1.500 8(4) nm, c=2.230 7(4) nm, β=99.55(1)°, and V=4.164 1(16) nm³，D_c=1.587 g·cm^-3. The complex contains two six-coordinated copper ions, and these two copper ions are connected together by L-aspartate to give rise to a binuclear structure. Hydrogen bonds and π-π stacking interactions are observed in the complex. CCDC: 249250.     

四元混配配合物[Ce(CH2=C(CH3)-COO)2(NO3)(phen)]2的合成、表征及晶体结构

A new complex with mixed-quadriligand [Ce(CH₂=C(CH₃)-COO)₂(NO₃)(phen)]₂ has been synthesized in aqueous solution of slight acidity and characterized by elementary analysis, IR and TGA. The crystal structure determination shows that the complex belongs to triclinic, space group P1, a=9.614?, b=10.047?, c=11.821?, Z=2, α=100.88(3)°, β=106.29(3)°, γ=97.93(2)°, V=1054(5)?³, D_c=1.741g·cm^-3, F(000)=546.00, μ(MoKα)=22.06cm^-1. And the crystal is consisted of a binuclear molecule. The coordina-tion of Ce³⁺ is nine.     

混配配合物[Zn(CF3COO)2(C7H6NS)2]的合成、晶体结构及表征

A mixed complex [Zn(CF₃COO)₂(C₇H₆NS)₂] was synthesized based on the reaction of Zn(CF₃COO)₂ and 2-aminobenzothiazol (C₇H₆NS) in methanol. The structure of the complex was characterized by elemental analysis, IR, ¹H NMR and thermal analysis. The crystal structure of the complex was determined by X-ray single crystal diffraction. The crystal belongs to monoclinic system with space group C2/c, a=3.174 3(9) nm, b=1.010 0(3) nm, c=1.723 1(5) nm, β=118.841(4)°, V=4.839(2) nm³; D_c=1.625 g·cm^-3; Z=8; F(000)=2 368; μ=1.266 mm^-1. CCDC: 600233.     

DBBD及其Cu(I)配位聚合物[CuI(DBBD)2]n的合成

In this article we report the synthesis of (R,S)-4,4′-biquinoline-6,6′-dimethyl-3,3′-dicarboxylate (DBBD) (1) and the formation of copper(I) coordination polymer [CuI(DBBD)₂]_n (2) by inducing a bidentate organic ligand (DBBD). The crystal 1 belongs to monoclinic system with space group P2₁, and a=0.881 30(19) nm, b=1.966 0(6) nm, c=1.478 1(4) nm, β=119.429(12)°, V=2.230 5(10) nm³, D_c=1.276 g·cm^-3. The crystal 2 belongs to orthogonal system with space group Fmm2, and a=2.044 41(17) nm, b=1.543 06(13) nm, c=1.652 45(13) nm, V=5.212 9(7) nm³, D_c=1.669 g·cm^-3, Z=8. CCDC: 292931, 1; 292934, 2.     

[Mn(NH2NHCO2C2H5)3](NO3)2的晶体结构和热分解机理

[Mn(ECZ)₃](NO₃)₂ is newly prepared by the aqueous solutions of Mn(NO₃)₂ and ethyl carbazate (ECZ). The crystal structure has been determined by X-ray crystal diffraction analysis. It belongs to monoclinic with space group of P2₁/n. The crystal parameters are: a=1.3974(2) nm, b=0.8796(2) nm, c=3.4322(7) nm, β=91.25(1) °, V= 4.2175(1) nm³, Z=8. Its molecular weight is 491.30. Mn²⁺ is located on the center of the molecular structure. Ethyl carbazate serves as a bidentate ligand which coordinates to the metal cations with its carbonyl oxygen atom and the terminal hydrazine nitrogen atom, forming five-member chelating rings, and three such rings are formed in each molecule. The coordination number of the metal ion is six and the coordination configuration of the central ion is octahedral. Specially, antimer configuration phenomenon is found in the molecule. The complex is further characterized by element analysis and IR measurements. The thermal decomposition mechanism is studied by using TG-DTG and DSC techniques. CCDC: 215675.     

配合物[Ce(CH2=C(CH3)COO)2(NO3)(Bipy)]的合成及晶体结构

The new complex [Ce(CH₂=C(CH₃)COO)₂(NO₃)(Phen)]₂ was prepared in ethanol-aqueous solution with 8-hydroxyquinoline as the acidity regulator. Its crystal structure was determined by X-ray diffraction analysis. The title complex is triclinic, space group P1, a=1.00832(3)nm, b=1.02858(8)nm, c=1.12350(8)nm, α=113.9250(10)°, β=103.8210(10)°, γ=81.4650(10)°, V=1.03252(14)nm³, Z=1, D_c=1.700g·cm^-3, F(000)=522. The coordination number of Ce³⁺ is nine. CCDC: 211278.     

多核银配位聚合物[Ag_2(BPE)(CF_3COO)_2]_n和{Ag_5(CF_3COO)_5[(CH_3)_3NCH_2COO]}_n的水热合成与晶体结构

<正>过渡金属配位聚合物因其丰富的网络拓扑结构及其在吸附、催化、分子识别、光、电、磁等方面的潜在应用而成为无机化学和材料化学研究领域中     

氧心羧桥异三核过渡金属簇合物[Fe2MO(CH3COO)6Py3].Py(1,M=Mn;2,M=Co;3,M=Ni)和[Fe2MO(CCl3COO)6(THF)3](4,M=Mn;5,M=Co;6,M=Ni)电子光谱的研究

The UV/VIS spectra for pyridine solution of complexes [Fe_2MO(CH_3COO)_6Py_2]·Py and THF solution of complexes Fe_2MO(CCl_3COO)_6(THF)_3 were studied. The d-d transitions were assigned and the ligand field parameters(B,D_q,β) were calculated for the related metal ions according to ligand field theory (Tanabe-Sugano diagram) in terms of O_h symmetry and reasonably good fits were obtained for the calculated and observed frequencies. The calculated results show that (1) the larger the ionic potential for M~(2+) ion, the larger the values of B, D_q for Fe~(3+) ion (2) the ligand field parameters of metal ions vary in parallel with the electronagativity of R in RCOO~-.     

镧系稀土四元配合物Ln(NO_3)_2(phen)_2(CH_3COCHCOCH_3)的合成及晶体结构表征

以乙酰丙酮(Hacac)、邻菲咯啉(phen)、硝酸根为配体,8-羟基喹啉为酸度调节剂合成出一个系列的镧系轻稀土四元配合物Ln(NO3)2(phen)2(CH3COCHCOCH3)(Ln=La,Ce,Pr,Nd,Sm)。配合物的结构与性质由元素分析,IR,1HNMR和TGA等表征。单晶Ce(NO3)2(phen)2(CH3COCHCOCH3)·H2O结构经由X射线衍射仪分析表明,晶体属单斜晶系,空间群P21/n,晶胞参数为a=1.11017(8)nm,b=0.98401(7)nm,c=1.34453(10)nm,β=102.0530(10)°,V=1.43641(18)nm3,Dc=1.715g·cm-3,Z=2,F(000)=742。配合物呈单核结构,中心离子Ce髥配位数为10。     

Fe3(CO)8(C6H5NC)(μ3-S)2的合成和晶体结构

The title compound Fe_3(CO)_8(C_6H_5NC)(μ_3-S)_2 (Ⅰ) was synthesized by the reaction of C_6H_5NCS with Fe_3(CO)_12 at room temperature. The crystal and molecular structure of the title compound were determined by single ctystal diffraction method. Crystal data: monoclinic, space group P2_1/C, a=12.718(4)Å, b=26.164(10) Å, c=l3.741(7) Å, β=117.18(2) °, V=4067(2) Å3, Z=8, Dc=1.825 g/cm3. The structure was solved by direct method and difference Fourier synthesis, and refined by full-matrix Least-squares with anisotropic thermal paramaters, using 1990 observed reflections [Ⅰ＞3σ(Ⅰ)].The final residual factor was R＝0.076, Rw＝0.082. The substituted ligand (C_6H_5NC)in Fe_3(CO)_8(C_6H_5NC)(μ_3-S)_2 is connected to the Fe(3) atom of the distorted tetragonal pyramid Fe_3S_2 framework.     

新型微孔磷酸铝[C4N2H14]2+[H2Al3P3O14]2-的合成、结构及相转变

以3-甲氨基丙胺为结构导向剂,在水热条件下合成了1个具有三维开放骨架结构的微孔磷酸铝化合物[C4N2H14][H2Al3P3O14](1),并通过X射线单晶衍射确定了其结构,用粉末X射线衍射(PXRD)、热重(TG)、元素分析(ICP及CHN)和扫描电子显微镜(SEM)对其进行表征.结果表明,化合物1属正交晶系,Pbca空间群,晶胞参数a=1.59839(11)nm,b=0.99402(6)nm,c=1.82261(11)nm,V=2.8958(3)nm3.化合物1的无机骨架由铝氧多面体(AlO5/AlO6)和磷氧四面体(PO4)严格交替连接构筑而成,形成了在[010]方向上具有一维十元环孔道的三维阴离子开放骨架.每个P原子通过桥氧原子与相邻的4个Al原子相连,而Al原子除了通过桥氧原子与相邻的4个P原子相连之外,还通过羟基的桥氧原子与1个或2个Al原子相连,分别形成五配位和六配位的Al.化合物1在550℃空气或氧气气氛下灼烧5 h后转变为具有ATV分子筛结构的微孔磷酸铝分子筛AlPO4-25,且一直稳定到800℃.     

二维Hofmann类双金属配合物Cu(DMF)_2[Pt(CN)_4]的合成及晶体结构(英文)

A two-dimensional cyanide-bridged Cu(Ⅱ)-Pt(Ⅱ) bimetallic complex has been synthesized by solution diffusion method using [Pt (CN)4]2- and [Cu (L)]2+ (L =3,10-diethanol-1,3,5,8,10,12-hexaazacyclotetradecane) as building blocks. Unexpectedly, the obtained complex Cu(DMF)2[Pt(CN)4] (1) is an analogue of the well-known Hofmann -type clathrate without macrocyclic ligand. Single-crystal X-ray diffraction reveals that 1 crystallizes in monoclinic, space group C2/m, a=1.624 8(6) nm, b=0.739 3(3) nm, c=0.695 5(3) nm, β=108.969(4)°. The crystal structure of 1 consists of two-dimensional corrugated metal cyanide sheets without interpenetration stacking along the a axis in an ABAB packing mode.     

2-氨基-5-硝基吡啶乙酸根桥联双核铜配合物的合成和晶体结构

2-氨基-5-硝基吡啶与Cu(CH3COO)2反应生成一个新的乙酸根桥联的双核铜配合物[Cu(CH3COO)2(C5H5N3O2)]2.2H2O.该配合物中,铜原子与一个吡啶环上N原子和四个乙酸根上O原子配位形成五配位的四方锥构型.其晶胞参数为:单斜晶系,空间群P21/c,a=0.834 5(8),b=2.001(2),c=0.808 1(8)nm,β=96.734(4)°,V=1.340(2)nm3,Z=2,Mr=657.37,Dc=1.629 g/cm3,F(000)=652,μ=1.663 mm-1,R1=0.060 4,wR2=0.126 4.电子吸收光谱在207 nm处有吸收;电子发射光谱在419 nm处有发射峰.并用IR和元素分析对配合物进行了表征.     

Fe3(CO)8[P[SC6H5)Cl2](μ3-S)2的合成和晶体结构

The title compound Fe_3(CO)_8 (P(SC_6H_5) Cl_2) (μ_3′-S)_2 was synthesised by reacting Fe_3(CO)_9 (μ_3-S)_2 with P (SC_6H_5) Cl_2. The crystal and molecular structure of the title compound has been determined by single crystal diffraction method. Crystal data: triclinic, space group P1, with a=0.7571(1), b=0.9097(1), c=1.7706(2) nm, α=95.03(1), β=101.79(1), γ=105.73(1)°, V =1.1359 nm, Z=2, Dc=1.935 g·cm~(-3). The structure was solved by direct method and difference Fourier synthesis, and refined by full-matrix least-squares with anisotropic thermal paramaters for non-hydrogen atoms, using 3724 observed reflections withI≥3σ(I). The final residual factor R=0.025, R_W=0.028.Fe_(CO)_8(P(SC_6H_5)Cl_2)(μ_3-s)_2 has a face-bridged 4e donors and the monosubstituted ligand is on the apical Fe atom.     

钼铁混合金属原子簇化合物[(η5-C5H5)4Mo4Fe2(μ3-S)5(CO)5]的合成和结构

(η~5-C_5H_5)_4Mo_4Fe_2(μ_3-S)_5(CO)_5 have been prepared from (η~5-C_5H_5)_2Mo_2(CO)_6 and Fe_8S_2(CO)_9 under toluene reflux for 14.5 hrs.The crystal and molecular structures of (η~5-C_5H_5)_4Mo_4Fe_2(μ_3-S)_5(CO)_5 were studied by X-ray structure analysis. The Crystallographic data are as follows: monoclinic, space group P2_1/n, unit cell: a=1.0589(4), b=1.7260(4), c=1.8963(4) nm, β=101.44(2)°, V=3.3967 nm, D_c=2.06 gcm~(-3) for Z=4, X-ray data were obtained over the range of 2°<2θ<50° via the ω-2θ scan mode with MoKα radiation on an Enraf-Nonius CAD4 diffractometer. The structure was solved by direct method (MULTAN) and refined by full matrix least-squares techniques for 3993 reflections with I>2σ(I), The final R=0.081. Figure 1 illustrates the configuration of the molecule (η~5-C_5H_5)_4Mo_4Fe_2(μ_3-S)_5(CO)_5, composing of a cubane-like (FeMo_3S_4) core and a trigonal pyramid (MoFe_2S) core, which linked by sharing Fe(1) atom.     

簇合物(μ-SC6H5)(μ-P(SC6H5)2)Fe2(CO)6的合成和晶体结构

用Fe_3(CO)_(12)与亚磷酸三硫代苯酯P(SC_6H_5)_3反应得到标题化合物。P(SC_6H_5)_3以其裂解分子片SC_6H_5和P(SC_6H_5)_2配位。用X-ray衍射技术测定了该化合物的晶体结构, 晶体属正交晶系, 空间群为Pbca, a=1.7422(7), b=1.0634(6), c=2.898(12) nm; V=5.370 nm, z=8, D_c=1.579 g·cm~(-3)。由直接法和差值Fourier合成解出全部非氢原子坐标, 并用全矩阵最小二乘法修正, 最后偏离因子R=0.054, R_w=0.058, 分子结构中心的Fe_2SP折叠环沿S…P线或沿Fe—Fe键折叠的二面角(分别为76.1°和82°)比其它具有中心Fe_2S_2, Fe_2P_2和Fe_2SP折叠环的类似化合物中的相应值小, Fe—Fe键长为0.2572 nm, Fe—S(1)—Fe=68.6°, Fe—P—Fe=70.7°。