Chloroaqua Complexes [M3S4(H2O)9?xClx](4?x)+ (M = Mo, W; x = 4, 6, 7) and Their Supramolecular Compounds with Cucur[8]uril

Compounds of trigonal cluster chloroaqua complexes with cucurbit[8]uril were synthesized by slowly evaporating HCl solutions of chalcogenides heterometallic cubane cluster complexes of molybdenum and tungsten with cucurbit[8]uril in air; the complexes were characterized by X-ray diffraction analysis: (H₃O)₈[Mo₃S₄(H₂O)_2.5Cl_6.5]₂Cl(PdCl₄)·(C₄₈H₄₈N₃₂O₁₆)· 29H₂O (a = 13.3183(17) Å, b = 13.7104(18) Å, c = 18.225(3) Å; α = 80.263(3)°, β = 77. 958(3)°, γ = 87.149(4)°, V = 3207.4(7) ų, space group P , Z = 1, ρ(calc) = 1.900 g/cm³), (H₃O)₄ [Mo₃S₄(H₂O)₃Cl₆]₂·(C₄₈H₄₈N₃₂O₁₆)₃·68H₂O (a = 21.413(6) Å, c = 49.832(10) Å; γ = 120°, V = 19788(8) ų, space group R , Z = 3, ρ(calc) = 1.695 g/cm³), (H₃O)₆ [Mo₃S₄(H₂O)₃Cl₆]₂Cl₂·(C₄₈H₄₈N₃₂O₁₆)·12H₂O (a = 15.881(2) Å, b = 17.191(2) Å, c = 23.276(4) Å; β = 98.865(15)°, V = 6278.7(15) ų, space group P2₁/c, Z = 2, ρ(calc) = 1.638 g/cm³), [W₃S₄(H₂O)₅Cl₄]₂·(C₄₈H₄₈N₃₂O₁₆)₃·35H₂O (a = 21.038(3) Å; α = 61.20(1)°, V = 6762.0(14) ų, space group R , Z = 1, ρ(calc) = 1.582 g/cm³). The [Mo₃S₄(H₂O)₃Cl₆]²⁻ anion complex was isolated as three geometrical isomers.Original Russian Text Copyright © 2004 by E. V. Chubarova, D. G. Samsonenko, H. G. Platas, F. M. Dolgushin, A. V. Gerasimenko, M. N. Sokolov, Z. A. Starikova, M. Yu. Antipin, and V. P. Fedin__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1049–1058, November–December, 2004.     

EPR study of solid solutions of [Cr(NH3)5Cl]x[Rh(NH3)5Cl]1?x[PdCl4]·nH2O and [Cr(NH3)5Cl]x[Rh(NH3)5Cl]1?x[PtCl4] compounds

In order to determine the features of the structure of double complex salts (DCSs) of [Cr(NH₃)₅Cl]×[MCl₄]·nH₂O, where M = Pd, Pt, n = 0, 1, the DCS solid solutions of palladium and platinum with isostructural DCSs containing the chloropentaammine rhodium cation, [Cr(NH₃)₅Cl] _x [Rh(NH₃)₅Cl]_1−x [MCl₄]·nH₂O, where x = 0.01–0.2, are synthesized and studied by the EPR method. DCSs with the isostructural chloropentaammine rhodium cation are used as a diluter for magneto concentrated systems. It is shown that DCS of platinum and anhydrous DCS of palladium have the identical environment of chromium ions. The EPR spectra of chromium ions for these compounds are described by the following spin Hamiltonian parameters: S = 3/2, g _xx = 1.987, g _yy = 1.987, g _zz = 1.985, D = 1660 Gs, E = 235 Gs. For the palladium complex containing crystalline water, the EPR spectra of chromium ions are described by the parameters: S = 3/2, g _xx = 1.984, g _yy = 1.984, g _zz = 1.984, D = 1060 Gs, E = 350 Gs. A decrease in the crystal field parameters for the aqueous palladium complex is caused by a redistribution of the electron density to the oxygen atom in the second sphere of the chromium ion environment.     

Structure and thermal properties of [Ir(NH3)5Cl]x[Rh(NH3)5Cl]1?xMO4 (x = 0.5, 1; M = Mo, W)

Complex salts [Ir(NH₃)₅Cl]x[Rh(NH₃)₅Cl]_1−x MO₄ (x = 0.5, 1; M = Mo, W) are synthesized and their thermal properties are studied. The crystal structures are determined for [Ir(NH₃)₅Cl]WO₄ and [Ir(NH₃)₅Cl]MoO₄. In the structures, the ions are linked by N-H...O hydrogen bonds, the shortest ones being 2.868(2)–3.422(2) ?. and 2.860(4)–3.434(3) ?. respectively. The thermal properties of the complex salts are studied in the hydrogen atmosphere and in hydrogen-helium mixtures. It is demonstrated that the final products are the mixtures of nanocrystalline powders of Ir and binary or ternary solid solutions with the hcp lattice.     

{[Cd(sulfadiazine)2]n [Cd(sulfadiazine)2·H2O]n}(英)

C om m ent Silver and zinc salts of sulfadiazine are widely used to prevent bacterial infection for both hum ans and anim als during burn treatm ents[1~4]. Because the slow release of the m etal ions highly relevant to the biologicalactivity ofthese polym…     

Crystal structure of K2[Mo3(PdPPh3)S4(C2O4)3(H2O)3]·0.5H2O

By the reaction of [Mo₃S₄(C₂O₄)₃(H₂O)₃]²⁻ with PdCl₂ and NH₄H₂PO₂ as a reducing agent, followed by the addition of PPh₃, a new oxalate cuboidal cluster complex [Mo₃(PdPPh₃)S₄(C₂O₄)₃(H₂O)₃]²⁻ is obtained. It was isolated and structurally characterized as K₂[Mo₃(PdPPh₃)S₄(C₂O₄)₃(H₂O)₃]·0.5H₂O. Original Russian Text Copyright ? 2008 by A. L. Gushchin, M. N. Sokolov, D. Yu. Naumov, and V. P. Fedin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 4, pp. 775–778, May–June, 2008.     

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.     

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.     

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.     

[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.     

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⁻.     

配合物Fe(pda)2(H2O)4和[FeCo(pda)4(H2O)4]n的合成与晶体结构

采用水热法合成了2个3-(3-吡啶基)丙烯酸的配合物:Fe(pda)2(H2O)4(1)和[FeCo(pda)4(H2O)4]n(2)(pda=3-(3-吡啶基)丙烯酸),用红外光谱、元素分析、热重-差热以及X-射线衍射单晶结构分析进行了表征.2个配合物都属于单斜晶系,配合物1的空间群为P21/n,配合物2的为P21/c.配合物1是一个pda配体中仅吡啶基氮原子参与配位、而羧基上的氧原子未参与配位的单核结构,通过大量的氢键作用形成三维超分子体系.2是pda配体桥联Fe和Co的异核二维层状配位聚合物;配体吡啶基上的氮原子和羧基上的氧原子都参与了配位,其中羧基采用单齿配位模式.     

Conductivity of La1 ? xSrxSc1 ? yMgyO3 ? α (x = y = 0.01–0.20) in reducing atmosphere

The ion and proton transfer numbers were measured by emf method in La_{1 − x} Sr _x Sc_{1 − y} Mg _y O_{3 − α} (x = y = 0.01–0.20) system in reducing hydrogen-containing atmosphere in the range of temperatures from 630 to 920°C and pH₂O from 0.61 to 2.65 kPa. Total ionic, proton, and oxygen conductivities of this system was measured as well. The electroconductivity measurements were carried out vs. pO₂ (from air to 10⁻¹⁴ Pa).     

一维链状配位聚合物[Cu3(TFSSB)2·(H2O)4·4H2O]n的合成和晶体结构

The title complex [Cu₃(TFSSB)₂·(H₂O)₄·4H₂O]_n (TFSSB=taurine 3-formylsalicylic schiff base) was synthesized by TFSSB and copper(Ⅱ) acetate monohydrate in ethanol solution and the crystal structure was determined by X-ray diffraction method. The crystal belongs to monoclinic system, space group P2₁ / n，with cell parameters: a=0.927 9(6) nm, b=1.173 0(2) nm, c=1.471(2) nm, β=106.96(2)°, and V=1.531(2) nm³, Z=2, D_c=1.890 g·cm^-3, μ=2.291 mm^-1, F(000)=882, R₁=0.025 9, wR₂=0.065 9. The Cu1 is five-coordinate, the Cu2 is four-coordinate. CCDC: 253298.     

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 nine-coordinate K[SmIII (Edta)(H2O)3] · 2H2O and Ten-Coordinate K2[SmIII(Pdta)(H2O)2]2 · 4.5H2O complexes

The title complexes, K[Sm^III(Edta)(H₂O)₃] · 2H₂O(I)(H₄Edta = ethylenediamine-N,N,N′,N′-tetraacetic acid) and K₂[Sm^III(Pdta)(H₂O)₂]₂ · 4.5H₂O (II) (H₄Pdta = propylenediamine-N,N,N′,N′-tetraacetic acid), were prepared and their compositions and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques, respectively. Complex I has a mononuclear structure, and the Sm³⁺ ion is nine-coordinated by an Edta ligand and three water molecules, yielding a pseudo-monocapped square antiprismatic conformation, and the complex crystallizes in the orthorhombic crystal system with space group Fdd2. The crystal data are as follows: a = 19.84(5), b = 35.58(9), c = 12.15(3) ?, V = 8580(38) ?³, Z = 16, ρ _c = 1.925 g/cm³, μ = 3.010 mm⁻¹, F(000) = 4976, R = 0.0252, and wR = 0.0560 for 3510 observed reflections with I ≥ 2σ(I). Complex II has a binuclear structure and the Sm³⁺ ion is ten-coordinated by a Pdta ligand, two oxygen atoms from a carboxylic group of adjacent Pdta ligand and two water molecules, yielding a distorted bicapped square antiprismatic prism. The complex crystallizes in the triclinic crystal system with space group P $ \bar 1 $ \bar 1 . The crystal data are as follows: a = 8.9523(15), b = 10.7106(15), c = 11.6900(19) ?, α = 80.613(5)°, β = 80.397(5)°, γ = 76.530(4)°, V = 1065.7(3) ?³, Z = 1, ρc = 1.970 g/cm³, μ = 2.532 mm⁻¹, F(000) = 1620, R = 0.0332 and wR = 0.0924 for 5390 observed reflections with I ≥ 2σ(I).     

[Ni(dien)2]2[Mn(NCS)6]·H2O的合成、晶体结构

The crystal of [Ni(dien)₂]₂[Mn(NCS)₆]·H₂O was synthesized and the structure of its single crystal was determined by X-ray diffraction. The crystal is monoclinic system, space group P2₁/c with a=16.544(3),b=15.137(2), c=17.334(3)?, β=99.90(1)°, V=4276.3(12)?³, Z=4, D_c=1.479g·cm^-3, M_r=951.55, F(000)=1998, μ=1.489mm^-1, R=0.0399, R_w=0.0958. IR was also determined.     

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).     

X-ray study of the thermolysis products of (NH4)2[OsCl6]x[PtCl6]1?x

Thermolysis of the complex salts (NH₄)₂[OsCl₆] _x [PtCl₆]_1−x (x = 0.25−0.9) formed nanocrystalline Os _x Pt_1−x phases. Pseudomorphism has been found: the habit of the single crystals of the starting salts is preserved during thermolysis, and the ∼10–20 nm metal particles are agglomerated into octahedral structures sized 5–10 μm.     

Synthesis and structures of nine-coordinate K[Dy(Edta)(H2O)3] · 3.5H2O, (NH4)3 [Dy(Ttha)] · 5H2O, and eight-coordinate NH4[Dy(Cydta)(H2O)2] · 4.5H2O complexes

The title complexes, K[Dy(Edta)(H₂O)₃] · 3.5 H₂O (I) (H₄Edta = ethylenediamine-N,N,N′,N′-tetraacetic acid), (NH₄)₃[Dy(Ttha)] · 5H₂O (II) (H₆Ttha = triethylenetetramine-N, N,N′,N″,N‴,N‴-hexaacetic acid), and NH₄[Dy(Cydta)(H₂O)₂] · 4.5H₂O (III) (H₄Cydta = trans-1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid), were prepared, and their compositions and structures were determined by elemental analyses and single-crystal X-ray diffraction techniques, respectively. In complex I, the Dy³⁺ ion is nine-coordinated by an Edta ligand and three water molecules, yielding a pseudo-monocapped square antiprismatic conformation, and the complex crystallizes in the orthorhombic crystal system with space group Fdd2. The crystal data are as follows: a = 19.751(7), b = 35.573(12), c = 12.227(4) ?, V = 8591(5) ?³, Z = 16, space group Fdd2 ρ_c = 1.877 g/cm³, μ = 3.742 mm⁻¹, F(000) = 4800, R = 0.0259, and wR = 0.0616 for 3218 observed reflections with I ≥ 2σ(I). For complex II, the Dy³⁺ ion is nine-coordinated by a Ttha ligand, yielding a pseudo-monocapped square antiprismatic conformation, and the complex crystallizes in the monoclinic crystal system with space group P2₁/c. In addition, there is a free non-coordinate carboxyl group (-CH₂COO⁻) in the [Dy(Ttha)]³⁻ complex anion. The crystal data are as follows: a = 10.353(3), b = 12.746(4), c = 23.141(7) ?, β = 91.005(5)°, V = 3053.2(15) ?³, Z = 4, space group P2₁/c ρ_c = 1.730 g/cm³, μ = 2.532 mm⁻¹, F(000) = 1620, R = 0.0332 and wR = 0.0924 for 5390 observed reflections with I ≥ 2σ(I). For complex III, the Dy³⁺ ion is eight-coordinated by a ligand Cydta and two water molecules, yielding a distorted square antiprismatic conformation, and the complex crystallizes in the triclinic system with space group P . The crystal data are as follows: a = 8.604(3), b = 10.012(4), c = 14.369(6) ?, α = 88.330(6)°, β = 75.363(6)°, γ = 88.285(6)°, space group P V = 1196.9(8) ?³, Z = 2, ρ_c = 1.776 g/cm³, μ = 3.194 mm⁻¹, F(000) = 644, R = 0.0445 and wR = 0.1041 for 3931 observed reflections with I ≥ 2σ(I). The article is published in the original.     

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].