Crystal structures of barium bis(iminodiacetato)cobaltates(III): [Ba(H2O)6][Co(Ida)2]2 · H2O and Ba4(H2O)14][Co(Ida)2]5(ClO4)3 · 5.46H2O · 2CH3OH

The structures of the crystals of Ba₄[trans(N)-Co(Ida)₂]₃[cis-(N)-Co(Ida)₂]₂(ClO₄)₃ · 19.46H₂O · 2CH₃OH (I) and Ba[trans-(N)-Co(Ida)₂]₂ · 7H₂O (II) (H₂Ida is iminodiacetic acid) were determin by X-ray diffraction. The crystals of I containing two geometric isomers of the complex anions [Co(Ida)₂]⁻ were obtained by a slow cooling of a hot solution, which contained initially only the cis-isomer. One Ba atom in I interacts with the trans-complex and with two cis-complexes to give a three-dimensional framework in crystal I. The positive charge of the last framework is compensated by one more trans-complex and by the perchlorate ions, one of which acts as a bidentate ligand with respect to the Ba atom. The crystals of II are built of the chains with the alternating Ba atoms and the trans-(N)-[Co(Ida)₂]⁻ anions. The other anions of the same structure are each “suspended” to the Ba atoms of the chain. Original Russian Text ? M. Zabel, A.I. Poznyak, V.I. Pawlowskii, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 11, pp. 831–836.     

［Mn2(CHZ)4(H2O)2］(PA)4·10H2O的制备和分子结构研究

本文论述了苦味酸(PA,三硝基苯酚)锰与碳酰肼(CHZ, NH₂NHCONHNH₂)反应制备目标配合物的方法及该配合物的晶体结构。该配合物的结构式为［O,O′-μ-Mn₂(CHZ)₄(H₂O₂)］(PA)₄·10H₂O。晶体属三斜晶系,P1 空间群。晶体学参数为：a=0.8269(1) nm, b=1.2812(1) nm, c=1.5915(1) nm; α=109.58(1)°, β=95.19(1)°, γ=92.76(1)°, V=1.5765(2)nm³; Z=1, Dc=1.580 g·cm^-3, μ(Mo K_α)=520 m^-1。晶体结构经全矩阵最小二乘法修正,最终偏离因子R=0.0557。该化合物为具有中心对称的双核配合物,以两个碳酰肼分子中羰基氧为桥原子将两个锰离子结合起来,与锰离子形成配位键的原子是碳酰肼分子第一、五氮原子,羰基氧原子和水分子中的氧原子,锰离子的配位数为七。若味酸根作为外界离子以库伦力和氢键与内界离子结合成配合物分子。     

N，N′-(2-苯并咪唑基甲基)亚氨基甲基膦酸的双核镍化合物Ni2(bbimp)2(4，4′-bipy)(H2O)2·2H2O和Ni2(bbimp)2(H2O)2][Ni(bbimp)(H2O)2]2·4H2O

该文报道了N，N′-(2-苯并咪唑基甲基)亚氨基甲基膦酸{bbimpH₂，[(C₇H₅N₂)CH₂]₂NCH₂PO₃H₂}的2个镍化合物Ni₂(bbimp)₂(4，4′-bipy)(H₂O)₂·2H₂O (1)和[Ni₂(bbimp)₂(H₂O)₂][Ni(bbimp)(H₂O)₂]₂·4H₂O (2)。化合物1是4，4′-联吡啶作为桥连配体的中性双核结构。化合物2含有1个中性的[Ni₂(bbimp)₂(H₂O)₂]双核分子与2个中性的[Ni(bbimp)(H₂O)₂]单核分子。双核分子单元中的2个Ni(Ⅱ)离子被2个膦酸氧桥连。在化合物2中，膦酸氧桥连的2个Ni(Ⅱ)离子之间存在铁磁性相互作用。     

[Pb2(TNR)2(CHZ)2(H2O)2]·4H2O和[Cd(CHZ)2(TNR)(H2O)]快速热分解过程的研究

利用温度跃升傅立叶变换红外原位分析技术在0.1MPa氩气的条件下，对斯蒂酚酸碳酰肼铅和斯蒂酚酸碳酰肼镉的快速热分解过程进行了研究。研究结果表明，斯蒂酚酸碳酰肼铅的主要热分解气体为NH₃, H₂O和 HONO，而斯蒂酚酸碳酰肼镉的主要热分解气体为CO 和 NO，因此斯蒂酚酸碳酰肼镉不满足作为环境友好起爆药的使用要求。这两种化合物在快速热分解过程中均产生金属异氰酸盐、金属碳酸盐和金属氧化物。利用Real程序计算其燃烧温度可得斯蒂酚酸碳酰肼铅的燃烧温度要高于斯蒂酚酸碳酰肼镉，对其燃烧产物进行计算，发现HNCO不在燃烧产物之列，NO的含量也比实验得出的浓度要小。     

[Gd2(Gly)6(H2O)4](ClO4)6(H2O)5的合成、晶体结构与热化学研究

利用微波技术合成了配合物[Gd₂(Gly)₆(H₂O)₄](ClO₄)₆(H₂O)₅, 进行了化学成分分析、红外表征和热重分析. 应用X衍射仪测定其晶体结构, 该晶体为一维链结构, 属三斜晶系, P 空间群, 晶胞参数: a＝1.1569(17) nm, b＝1.4138(2) nm, c＝1.5642(2) nm, α＝96.910(2)°, β＝102.735(2)°, γ＝105.512(2)°, V＝2.3606(6) nm³, Z＝2, D_c＝2.144 g•cm^－3. 采用精密溶解-反应量热计, 通过设计热化学循环, 计算出了该配合物的标准摩尔生成焓为 －(7960.73±3.23) kJ•mol^－1.     

Synthesis, structure, and thermal decomposition of [H2(4,4′-Bipy)][In(H2O)2(NCS)4]2 and [HUr]2[In(H2O)(NCS)5] · 2H2O

The reaction of indium thiocyanate with bipyridine (4,4-Bipy) and urotropine (Ur) gave [H₂(4,4′-Bipy)][In(H₂O)₂(NCS)₄]₂ (I) and [HUr]₂[In(H₂O)(NCS)₅] · 2H₂O (II), which were identified using elemental analysis, IR spectra, and thermogravimetric analysis. The thermal decomposition of compound I and II ends at 650 and 640°C, respectively, and gives In₂O₃. X-Ray diffraction analysis of compound I showed that complex anions in the crystal form chains through O-H…S hydrogen bonds. The anion chains form a close packing of columns with bipyridine cations located in the voids. Original Russian Text ? S.P. Petrosyants, A.B. Ilyukhin, V.A. Ketsko, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 6, pp. 951–955.     

配位化合物[Cd(hca)2(H2O)3](H2O)2，[Cu(hca)2(phen)]的合成与表征

配合物1由醋酸镉和Nahca(对羟基肉桂酸钠)在水溶液中反应得到,配合物2由醋酸铜,Hhca和phen在水和乙醇混合溶液中反应得到。配合物1属正交晶系,Pbcn空间群。配合物2属单斜晶系,C2/c空间群。配合物1和2中配体中的羧酸根与金属离子都是螯合配位的,末端羟基没有参与配位。配合物1和2的结构中都包含了丰富的氢键。通过氢键作用,配合物1形成了三维网状超分子结构,配合物2形成了二维层状超分子结构。     

Syntheses of the eight-coordinate NH4[ErIII(Cydta)(H2O)2] · 4.5H2O and (NH4)2[Er 2III (Pdta)2(H2O)2] · 2H2O complexes and their structural investigation

In this work, the title complexes, NH₄[Er^III(Cydta)(H₂O)₂] · 4.5H₂O (I) (H₄Cydta = trans-1,2-cyclo-hexanediamine-N,N,N′,N′-tetraacetic acid) and (NH₄)₂[Er₂^III(Pdta)₂(H₂O)₂] · 2H₂O (II) (H₄Pdta= propylene-diamine-N,N,N′,N′-tetraacetic acid), were prepared, respectively, and their composition and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques. Complex I selects a mononu-clear structure with pseudosquare antiprismatic geometry crystallized in the triclinic crystal system with space group $ P\bar 1 $ P\bar 1 and the central Er³⁺ ion is eight-coordinated by the hexadentate Cydta ligand and two water molecules. The crystal data are as follows: a = 8.568(3), b = 10.024(3), c = 14.377(4) ?, α = 88.404(4)°, β = 75.411(4)°, γ = 88.332(4)°, V = 1194.2(6) ?³, Z = 1, ρ _c = 1.793 g/cm³, μ = 3.586 mm⁻¹, F(000) = 648, R = 0.0257, and wR = 0.0667 for 4169 observed reflections with I ≥ 2σ(I). Complex II is eight-coordinated as well, which selects a binuclear structure with two pseudosquare antiprismatic geometry and crystallizes in the monoclinic crystal system with space group P2₁/n. The central Er³⁺ ion is coordinated by two nitrogens and four oxygens from one hexadentate Pdta ligand. Besides, two oxygens come from one carboxylic group of the neighboring Pdta ligand and one water molecule, respectively. The crystal data are as follows: a = 12.7576(8), b = 9.3151(6), c = 14.3278(9) ?, β = 96.1380(10)°, V = 1692.93(19) ?³, Z = 4, ρ _c = 2.054 g/cm³, μ = 5.015 mm⁻¹, F(000) = 1028, R= 0.0228, and wR = 0.0534 for 2984 observed reflections with I ≥ 2σ(I).     

[U(CO3)3(H2O)2]·2H2O配合物的合成及晶体结构

A uranylcontaining compound [U(CO₃)₃(H₂O)₂]·2H₂O has been synthesized under hydrothermal condition and characterized by X-ray single-crystal analysis. Crystal structural analysis indicates that this compound consists of three CO₃^2- molecules, one U⁶⁺. The results reveal that the title compound presents a 3D frame work built up by O-H…O week hydrogen bonds interactions. The central uranium atom is eight-coordinated through three CO₃^2- molecules and two H₂O. The compound shows a coplanar hexagonal network structure, each hexagon containing a hexagonal hole with a water moleculet. CCDC: 737313.     

三维超分子[Ni(hmt)2(SCN)2(H2O)2][Ni(SCN)2(H2O)4](H2O)2的自组装,晶体结构及磁性质(hmt=六次甲基四胺)

Compound [Ni(hmt)₂(SCN)₂(H₂O)₂][Ni(SCN)₂(H₂O)₄](H₂O)₂ (hmt=hexamethylenetetramine) was pre-pared and structurally characterized by means of X-ray single crystal diffraction. The two neutral units [Ni(hmt)₂(SCN)₂(H₂O)₂] and [Ni(SCN)₂(H₂O)₄] are joined together through hydrogen bonds N…H-O, O…H-O and S…H-O. In the solid state, the compound has three-dimensional network structure. The determination of its variable-temperature magnetic susceptibilities (5～300K) shows that the magnetic behavior obeys the Curie-Weiss law over the whole temperature ranges.