Crystal structure of [Pd(NH3)4]3[Ir(NO2)6]2·H2O

A single crystal of [Pd(NH₃)₄]₃[Ir(NO₂)₆]₂·H₂O double complex salt is studied by X-ray diffraction. Crystallographic characteristics are as follows: a = 21.0335(5) ?, b = 8.0592(2) ?, c = 21.3452(5) ?, β = 91.254(1)°, V = 3617.43(15) ?³, P2₁/c space group, Z = 4, d _x = 2.714 g/cm³. Single-layer pseudohexagonal packing of complex anions is determined along the [−1 0 1] direction in the structure. Complex cations and crystallization water molecules are located between the mentioned layers.     

trans-dinitro- and trans-dinitratoruthenium complexes [RuNO(NH3)2(NO2)2(OH)] and [RuNO(NH3)2(H2O)(NO3)2]NO3·H2O

Methods for the synthesis of trans-diammino complexes [RuNO(NH₃)₂(NO₂)₂(OH)] (I) and [RuNO(NH₃)₂(H₂O)(NO₃)₂](NO₃)·H₂O (II) are suggested. The compounds were studied by IR spectroscopy and X-ray phase and X-ray structural analyses. Crystal data: space group P-1; a = 6.2328(2) ?, b = 11.0488(3) ?, c = 11.0981(4) ?, α = 71.942(1)°, β = 83.291(1)°, γ = 86.877(1)° (I); space group P2₁; a = 6.6290(2) ?, b = 13.4389(5) ?, c = 7.0180(2) ?, β 114.281(1)° (II). Complex II readily lost some part of crystal water on storage in open air. Original Russian Text Copyright ? 2009 by M. A. Il’in, E. V. Kabin, V. A. Emel’yanov, I. A. Baidina, and V. A. Vorob’yov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 341–348, March–April, 2009.     

Double complex salts [Pd(NH3)4]3[Rh(NO2)6]2, [Pd(NH3)4]3[Rh(NO2)6]2·H2O as promising precursors to prepare Pd-Rh nanoalloys

Two new double complex salts [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂ (I) and [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂·H₂O (II) are synthesized and characterized. The techniques to produce one-phase residues of the salts are developed. The crystallographic data for I: a = 18.915(2) ?, V = 6767.4 ?³, F-43c space group, Z = 8, d _x = 2.548 g/cm³; II: a = 21.160(6) ?, b = 8.085(7) ?, c = 21.363(4) ?, β = 91.71(4)°, V = 3661.1(6) ?³, P2₁/c space group, d _x = 2.357 g/cm³. Thermal properties of the obtained compounds in the hydrogen and helium atmosphere are studied. It is shown that the final product of their decomposition both in the inert and reducing atmosphere is a powder consisting of bimetallic nanosized particles (nanoalloy) of Pd_0.59Rh_0.41 (Fm-3m space group, a = 3.856(2) ?, crystallite size of 8–11 nm).     

配合物[Cr3(μ3-O)(Tc)6(H2O)3]·(NO3)·4H2O的水热合成及晶体结构

通过有限个过渡金属离子如Fe,Ni,Cr,Mn与O、OH、-O或-O2CR等桥联原子或基团键合形成的具有不同尺寸的环形轮状金属离子簇合物或分子簇合物是近年来的研究热点之一[1,2].它们不仅具有独特的结构,而且在催化、非线性光学、分子自组装等方面具有潜在的应用价值[3～5].特别是具有三角型结构的过渡金属-氧轮簇化合物由于可以作为单分子磁体的磁性交换和电子耦合的研究体系,引起了研究人员的极大地兴趣[6,7].研究表明,具有[M(μ3-O)(O2CR)6L3]0/+,(M=Fe3+或Mn3+,L为水或吡啶,R为烷基或芳香基团)结构的化合物具有反铁磁作用[8,9].     

Mixed-ligand complexes [Cd(DMSO)5(NCS)][Cr(NH3)2(NCS)4] · 3DMSO and [Mn(DMSO)4(H2O)2][Cr(NH3)2(NCS)4]2 · 6DMSO · 2H2O: Syntheses and crystal structures

New mixed-ligand coordination compounds[Cd(DMSO)₅(NCS)][Cr(NH₃)₂(NCS)₄] · 3DMSO (I) and [Mn(DMSO)₄(H₂O)₂][Cr(NH₃)₂(NCS)₄]₂ · 6DMSO · 2H₂O (II) have been synthesized and studied by IR spectroscopy and X-ray diffraction analysis. The crystals of compound I are monoclinic, a = 14.5275(7), b = 23.1692(11), c = 14.6969(6) ?, β = 97.057(2)°, V = 4909.4(4) ?³, space group P2₁/c, Z = 4, ρ_calcd = 1.507 g/cm³, R = 0.0556. The crystals of compound II are triclinic, a = 11.7784(3), b = 12.1760(3), c = 13.1922(2) ?, α = 85.5420(10)°, β = 87.9000(10)°, γ = 70.3680(10)°, V = 1776.46(7) ?³, space group P , Z = 1, ρ_calcd = 1.444 g/cm³, R = 0.0350. Original Russian Text ? E.A. Gerasimova, T.V. Utkina, E.V. Peresypkina, A.V. Virovets, T.G. Cherkasova, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 5, pp. 751–755.     

Cu(NO3)2(La(NO3)3)-CO(NH2)2-H2O三元体系的等温溶度研究

本文首次报道三元体系Cu(NO₃)₂-CO(NH₂)₂-H₂O(30℃)和La(NO₃)₃-CO(NH₂)₂-H₂O(25℃)的等温溶度及饱和溶液、折光率,绘制相应的溶度图及折光率-组成图。体系中发现有组成为Cu(NO₃)₂·4CO(NH相似文献   

Structure of complex salts [Co(NH3)6][Rh(NO2)6] and [Co(NH3)6][(NO2)3Rh(μ-NO2)1+x(μ-OH)2?xRh(NO2)3]·(2-x)(H2O), x = 0.17

The structures of two salts [Co(NH₃)₆][Rh(NO₂)₆] (I) and [Co(NH₃)₆][(NO₂)₃Rh(μ-NO₂)_1+x (μ-OH)_2−x Rh(NO₂)₃]·(2−x)(H₂O), x = 0.17 (II) are solved. Single crystals of the salts are obtained by the counter diffusion method through the gel of aqueous solutions of [Co(NH₃)₆]Cl₃ and Na₃[Rh(NO₂)₆]. The structure of [Co(NH₃)₆][Rh(NO₂)₆] is consistent with the diffraction data for a polycrystalline sample of poorly soluble fine salt formed in the exchange reaction between aqueous solutions of [Co(NH₃)₆]Cl₃ and Na₃[Rh(NO₂)₆]. The structure of [Co(NH₃)₆][(NO₂)₃Rh(μ-NO₂)_1+x (μ-OH)_2−x Rh(NO₂)₃]·(2−x)(H₂O), x = 0.17 exhibits the stabilizing effect of a large cation in the formation of novel, unknown previously coordination ions: [(NO₂)₃Rh(μ-NO₂)(μ-OH)₂Rh(NO₂)₃]³⁻ and [(NO₂)₃Rh(μ-NO₂)₂(μ-OH)Rh(NO₂)₃]³⁻.     

［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。     

Oxidative cleavage of α-sulfonyl ketones to carboxylic acids with Ce(NH4)2(NO3)6

Tandem oxidative cleavage of α-sulfonyl arylketones 2 with the combination of Ce(NH₄)₂(NO₃)₆ and O₂ in MeCN afforded carboxylic acids 3 in moderate to good yields. The plausible reaction mechanism has been discussed.     

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.     

Crystal structure of metal-organic coordination polymers [Cu(bpy)2(H2O)2](NO3)2·4.5C2H5OH and [Cu2(bpy)(H2O)(L-pha)2](NO3)2·H2O

Two metal-organic coordination polymers [Cu(bpy)₂(H₂O)₂](NO₃)₂·4.5C₂H₅OH (1) and [Cu₂(bpy)(H₂O)(L-pha) ₂](NO₃)₂·H₂O (2) (L-Hpha = L-phenylalanine, bpy = 4,4′-bipyridyl) are prepared by slow evaporation of an aqueous alcoholic solution of copper nitrate, L-phenylalanine, and 4,4′-bipyridyl. The structure and composition of the obtained compounds are determined by single crystal XRD. The framework of compound 1 is positively charged and forms two types of intersecting channels. Compound 2 is a homochiral metal-organic coordination polymer whose structure contains L-phenylalanine anions.     

四元体系LiNO3-Mg(NO3)2-NH4NO3-H2O相图预测及相关相变储能材料的研究

应用修正的BET热力学模型对Mg(NO3)2-NH4NO3-H2O三元体系和LiNO3-Mg(NO3)2-NH4NO3-H2O四元体系在273～320 K的相图进行预测,并找到一个相变温度较低的四元共晶点Mg(NO3)2.6H2O-LiNO3.3H2O-NH4NO3,其质量百分数组成为:25.5%的硝酸铵,28.4%的硝酸锂,13.8%的硝酸镁和32.3%的水,通过实验对共晶点组成材料的吸放热行为进行测定,发现其熔化温度为286.3 K,且DSC测试其相变热焓为192.7 J.g-1,表明该材料可用作潜在的低温相变储能材料。     

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.     

Synthesis and structures of Cs4[(UO2)2(C2O4)(SO4)2(NCS)2] · 4H2O and (NH4)4[(UO2)2(C2O4)(SO4)2(NCS)2] · 6H2O

Single crystals of Cs₄[(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂] · 4H₂O (I) and (NH₄)₄[(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂] · 6H₂O (II) have been synthesized and studied by X-ray diffraction. The crystals of both compounds are orthorhombic with the space group Pbam, Z = 2, and unit cell parameters a = 12.0177(3) ?, b = 18.6182(5) ?, c = 6.7573(10) ?, R = 0.0376 (I); a = 11.6539(9) ?, b = 18.3791(13) ?, c = 6.7216(5) ?, R = 0.0179 (II). The main structural units of crystals I and II are [(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂]⁴⁻ chains belonging to the crystal-chemical group A₂K⁰²B₂²M₂¹ (A = UO₂²⁺, K⁰² = C₂O₄²⁻, B² = SO₄²⁻, M¹ = NCS⁻) of the uranyl complexes. The uranium-containing chains are joined into a three-dimensional framework due to a system of electrostatic interactions with the cesium or ammonium ions in the structure of I. In the structure of II, this framework is additionally stabilized by hydrogen bonds involving the outer-sphere water molecules and ammonium ions. Original Russian Text ? I.V. Medrish, A.V. Virovets, E.V. Peresypkina, L.B. Serezhkina, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 7, pp. 1115–1120.     

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).     

LaL3(NO3)3·(H2O)2·(C2H5OH)2的晶体结构和生成反应焓变

0 引言 稀土是一类具有特殊结构和性质的元素,稀土元素不仅大量用于工业,而且在农业和医学领域也有广泛应用 [1,2].其中,镧系离子以其独特的光、电、磁、催化和分析等性能而受到人们的广泛关注,并进行了大量的研究.镧系离子本身发光效率低,目前,设计并合成含有稀土离子La3+和Eu3+的超分子配合物,作为发光分子器件和荧光探针成为稀土配位化学,材料科学,超分子化学,分析化学和生物化学等研究领域的热点课题之一 [3～8].但对它们的热化学行为的研究鲜见文献报道.     

Crystal structure of a tetrahedral cluster complex [Zn2(NH3)6(μ-OH)][Zn(NH3)4]0.5[Re4Te4(CN)12]·5H2O

A cluster complex of the composition [Zn₂(NH₃)₆(μ-OH)][Zn(NH₃)₄]_0.5[Re₄Te₄(CN)₁₂]·5H₂O is obtained by the interaction of an aqueous solution of K₄[Re₄Te₄(CN)₁₂]·5H₂O with an aqueous ammonia solution of ZnCl₂. The compound crystallizes in the C2/m (12) monoclinic space group with unit cell parameters a = 23.233(2) ?, b = 14.5906(16) ?, c = 14.3825(15) ?, β = 125.169(1)°, V = 3985.5(7) ?³, Z = 4, d _x = 3.290 g/cm³. The structure is built from cluster [Re₄Te₄(CN)₁₂]⁴⁻ anions and complex [Zn₂(NH₃)₆(μ-OH)]³⁺ and [Zn(NH₃)₄]²⁺ cations; the latter is disordered over two positions.     

一个新的Tutton盐Na2[Co(H2O)6](SO4)2的结构与性能研究

采用溶液法合成了一个新的Tutton盐Na2[Co(H2O)6](SO4)2通过红外光谱和X-射线单晶衍射对其进行了表征.晶体结构分析表明该化合物晶体属单斜晶系,P21/c空间群,晶胞参数:a=0.6185(2)nm,b=1.2334(3)um,c=0.9137(1)nm,β=105.775(1)°,V=0.67078(2)nm3,Z=2.固体粉末紫外可见透射光谱是不连续的,具有较高的透过率和较窄的带宽(300～450 nm).用循环伏安法研究了化合物的电化学性质,发现Na2[Co(H2O)6](SO4)2掺杂氢氧化镍电极片的氧化还原峰电流均有较大提高,电极反应活性明显增加.     

Structure and luminescence of [Tb0.5(C6NO2H5)3(H2O)2]2n·(H3O)4n(ZnCl5)n(ZnCl4)2n

A novel bimetallic 4f-3d metal-isonicotinic acid inorganic-organic hybrid complex [Tb_0.5(C₆NO₂H₅)₃(H₂O)₂]_2n ·(H₃O)_4n (ZnCl₅) _n (ZnCl₄)_2n (1) is synthesized. It has a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that it displays interesting emissions in the violet, blue, green, and yellow regions.     

[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.