K_3[Gd~Ⅲ(nta)_2(H_2O)]·6H_2O和(NH_4)·[Gd~Ⅲ(Cydta)(H_2O)_2]·5H_2O的合成及晶体结构

Two new Gd Ⅲ complexes with nitrilotriacetic acid(nta) and trans-1,2-cyclohexanediaminetetraacetic acid(Cydta) ligands were synthesized. Their crystal structures were determined by single-crystal X-ray structure analyses. The crystal data are as follows: K 3[Gd Ⅲ(nta) 2·(H 2O)]·6H 2O, monoclinic system, C2/c space group, a=1.534 81(15) nm, b=1.292 05(12) nm, c=2.610 8(3) nm, β=96.244(2)°, V=5.146 7(9) nm 3, Z=8, M=776.87, D c=2.005 g/cm 3, μ= 3.149 mm -1 and \{F(000)=\}3 080, R=0.024 5, wR=0.064 3 for 4 455 unique reflections and R= 0.028 9, wR=0.067 2 for all 10 305 reflections. The Gd ⅢN 2O 7 part in the [Gd Ⅲ(nta) 2(H 2O)] 3- anion is a pseudo-monocapped square antiprismatic nine-coordination structure.(NH 4)[Gd Ⅲ(Cydta)(H 2O) 2]·5H 2O, triclinic system, P1 space group, a=0.866 2(3) nm, b=1.006 7(3) nm, c= 1.444 8(5) nm, α= 88.282(5)°, β=75\^190(5)°, γ=88.317(4)°, V=1.217 2(7) nm 3, Z=2, M=643.69, D c=1.756 g/cm 3, μ=2.798 mm -1 and F(000)=650, R=0.030 3, wR=0.080 9 for 4 273 unique reflections and R=0.033 2, wR=0.082 5 for all 5 062 reflections. The Gd ⅢN 2O 6 part in the [Gd Ⅲ(Cydta)(H 2O) 2] - anion has a pseudo-square antiprismatic eight-coordination structure.

[Cu_3(μ_(10)-bta)(μ_2-C_2O_4)(H_2O)_2]_n的水热合成与结构表征

有机-无机杂化材料因其在催化、化学吸附、磁性和电子导体等方面具有广泛的应用而成为人们的研究热点。通过过渡金属离子和特殊的有机配体之间的反应,一系列具有独特结构的配位聚合物已被合成出来。多齿有机配体可螯合两个或多个金属离子,这些金属离子之间存在良好的电子交换,可形成一维、二维或三维的配位聚合物。

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HoIII离子氨基多羧酸 (nta =氨基三乙酸 ,cdta =反式 1,2 环己二氨四乙酸 )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K3[Ho(nta) 2 (H2 O) ]·5H2 O ,单斜晶系 ,C2 c空间群 ,a =1 5 36 4 (8)nm ,b =1 2 881(7)nm ,c=2 6 16 3(13)nm ,β =96 .14 0 (9)°,V =5 4 16 (5 )nm3,Z =8,Dc=1 932g cm3,μ=3 6 35mm- 1 和F(0 0 0 ) =2 94 4 .其R和Rw 值分别为 0 0 310和 0 0 6 75 (对 4 5 0 9个独立的衍射点 ) ,R和Rw 值分别为0 0 4 4 2和 0 0 70 7(对所有 10 336个衍射点 ) .K3[Ho(nta) 2 (H2 O) ]·5H2 O配合物中 ,HoIIIN2 O7部分是一个九配位单帽四方反棱柱体结构 .(b)分子式NH4 [Ho(cdta) (H2 O) 2 ]·4 5H2 O ,三斜晶系 ,P 1,空间群 ,a =0 .86 36 (3)nm ,b =1 0 0 72(3)nm ,c=1 4 4 5 7(5 )nm ,α =88 382 (5 )° ,β=75 2 75 (5 )°,γ =88 382 (5 )° ,V =1 2 15 4 (7)nm3,Z =2 ,Dc=1 6 5 7g cm3,μ =3 315mm- 1 和F(0 0 0 ) =6 0 6 .其R和Rw 值分别为 0 0 2 83和 0 0 70 8(对 4 2 0 3个独立的衍射点 ) ,R和Rw 值分别为 0 0 32 5和 0 0 730 (对所有 4 5 95个衍射点 ) .NH4 [Ho(cdta) (H2 O) 2 ]·4 5H2 O配合物中HoIIIN2 O6 部分是一个八配位四方?

Synthesis and Structural Characterization of Mononuclear Mn^(II) Picolilato Complex Mn(2-C_5H_4NCOO)_2(H_2O)_2.1/2CH_3CN

A Mn(II) picolilato complex Mn(2-C5H4NCOO)2(H2O)2?/2CH3CN 1 has been synthesized. Crystal of 1 is of monoclinic, space group C2/c with a = 25.6613(3), b = 8.6357(2), c = 16.8286(2) ? b = 122.835(1), V = 3133.47(9) ?, Mr=355.7, Dc = 1.508 g/cm3, F(000) = 1456, m = 0.874 cm1 and Z = 8. The final refinement gave R = 0.0362 and wR = 0.1096 for 2264 reflections (I > 2s(I)). The Mn(II) atom possesses distorted octahedral coordination geometry and the structural parameters around the Mn ion are close to those of other Mn analogues. Extensive hydrogen bonding interactions between carboxylate and H2O were observed making one-dimensional chains of the Mn monomers.

Preparation and Crystal Structure of Hetero-metal Clusters [η~5-C_5H_4C(O)CH_2CH_2C(O)OCH_3]FeCoM(μ_3-S)(CO)_8 (M = Mo or W)

The hetero-metal clusters [■5-C5H4C（O）CH2CH2C（O）OCH3]FeCoM（■3-S）（CO）8 （M = Mo 1, M = W 2） were prepared by thermal reactions of FeCo2（CO）9(（3-S） with metal exchange reagent [■5-C5H4C（O）CH2CH2C（O）OCH3]M（CO）3Na （M = Mo or W） in THF. Cluster 1 reacted with 2,4-dinitrophenylhydrazine at room temperature to yield the cluster hydrazone derivative (（3-S）CoFeMo（CO）8[(5-C5H4C（NR）Me] [R = NHC6H3-2,4-（NO2）2] 3. All the compounds were characterized by elemental analyses, IR and NMR spectra. Cluster 1 was determined by single crystal X-ray diffraction. Crystal data: C18H11O11SCoFeMo, Mr = 646.05, triclinic, space group P, a = 8.148（2）, b = 10.685（3）, c = 13.410（4） ?, ( = 100.077（5）, ( = 102.452（5）, ( = 91.108（6）(, V = 1120.4（5） ?3, Z = 2, Dc = 1.915 g/cm3, F（000） = 636, ( = 2.071 mm(1, the final R = 0.0378 and wR = 0.0968 for 5074 observations with (I > 2（（I））.

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex:[NdFe(CN)_6(DMF)_4(H_2O)_3]H_2O

A new bimetallic cyano-bridged complex, [NdFe(CN)6(DMF)4(H2O)3]H2O (DMF = N,N-dimethylformamide) 1, has been obtained by the reaction of hexacyanoferrate potassium with neodymium (Ⅲ) chloride in H2O/EtOH/DMF (volume ratio: 2:2:1), and its structure was determined by means of single-crystal X-ray diffraction. The compound crystallizes in space group P21/n of monoclinic system with cell parameters: a = 17.646(1), b = 8.9011(3), c = 19.945(1) ? b = 95.835(2)? V = 3116.6(3) ?, Z = 4, Dc = 1.536 g/cm3, Mr = 720.66, F(000) = 1456, m = 2.166 mm-1, R = 0.0386, wR = 0.1120 and S = 1.061. The central Nd (Ⅲ) ion is coordinated by seven oxygen atoms of four DMF molecules and three water molecules and one nitrogen atom of the bridging cyanide in a slightly distorted square-antiprism arrangement, and the Fe (Ⅲ) ion is in an almost octahedral environment coordinated to six cyano-ligands, of which one cyanide ligand bridges the Nd (Ⅲ) ion to form a bimetallic complex. Molecules of complexes in the crystal lattice are held together by hydrogen bonding, forming a three-dimensional framework.

Crystal Structure Analysis of Tetras[L-tris(ethylenediamine) cobalt(Ⅲ)] tris[hexacyanoruthenate(Ⅱ)]

The crystal of the title compound, [Co(en)3]4[Ru(CN)6]310H2O (en = ethylenediamine, C2H8N2), is formed from the octahedral cations of Co(en)33+ and anions of Ru(CN)64. The Co atom is coordinated to six nitrogen atoms of ethylenediamines in a L configuration and the Ru atom is also coordinated to six carbon atoms of cyanides. There is no bridging-cyanide between the metal ions in the structure. The crystal is of monoclinic, space group P21/c with a = 17.686(4), b = 14.496(4), c = 18.019(7) ? b = 116.07(2), V = 4150(2) 3, Z = 2, Mr = 1908.60, C42H116N42O10Co4Ru3, m(MoKa) = 1.391 mm1, Dc = 1.527 g/cm3, F(000) = 2084, R = 0.0520 and wR = 0.1070 for 5443 observed reflections (I > 2s(I)).

Synthesis and Crystal Structure of Dicopper(II) Compound Containing Oxalate and Reduced Imino Nitroxide Radicals

A new dicopper(II) compound with oxalate and reduced imino nitroxide radicals [Cu2(m-C2O4)(Him2-py)2(H2O)2](NO3)2 (Him2-py=1-hydroxy-2-(2-pyridyl)-4,4,5,5-tetramethyli- midazoline) has been synthesized and its crystal structure was determined by X-ray diffraction method. The complex crystallizes in monoclinic, space group P21/n with a = 9.913(4), b = 19.057(8), c = 10.169(4) ? b = 114.292(7), V = 1751(1) 3, C26H38Cu2N8O14, Mr = 813.72, Dc = 1.543 g/cm3, m(MoKa) = 1.290 mm-1, F(000) = 840, Z = 2, the final R = 0.0398 and wR = 0.0986 for 1878 observed reflections (I>2s(I)). The imino nitroxide 2-(2-pyridyl)-4,4,5,5-tetramethyl- imidazoline-1-oxyl (im2-py) is reduced in the reaction to yield Him2-py which consists of oxalato-bridged centrosymmetric [Cu2(m-C2O4)(Him2-py)2(H2O)2]2+ ions and noncoordinated NO3- anions. Each copper(II) ion is in a distorted tetragonal pyramid environment: two nitrogen atoms from Him2-py and two oxygen atoms from the oxalate group are in the basal plane, and one water molecule at the axial position.

无机阴离子对UV-铁(Ⅲ)-丙二酸体系的影响

分析了3种常见的无机阴离子(SO2-4、Cl-、NO-3)对UV-铁(Ⅲ)-丙二酸体系中铁价态转化和邻苯二甲酸二甲酯(DMP)降解率的影响以及两者之间的机理联系。在pH=3、高氯酸铁与丙二酸配比为1∶10的条件下进行光降解。结果表明,在UV-铁(Ⅲ)-丙二酸体系中,无机阴离子不但对铁价态之间的转化有显著影响,而且对DMP的降解也有一定影响。在探讨无机阴离子对铁价态之间的转化影响的研究中,分别以存在与不存在DMP两种条件下进行讨论。在探讨无机阴离子对DMP的影响研究中,结果表明,无机阴离子对DMP的降解作用表现为:SO2-4和NO-3对DMP的降解率有微弱的促进作用,而Cl-对DMP的降解率无显著影响。