[COH(NH2)2]2[Cu(pic)2(ClO4)2]的合成与晶体结构

The title compound was synthesized by reaction of Cu(ClO₄)₂， picolinic acid and carbamide in C₂H₅OH/CH₃CN solution， and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system， space group Pbca with a=14.0481(8)， b=9.0130(5)， c=18.626(1)?， V=2358.3(2)?³， Z=4， D_x=1.771g·cm^-3， μ=1.235mm^-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane， while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances， resulting in a 4+2 elongated octahedral environment. In the compound， there also exist two protonated carbamide cations for charge balance. CCDC： 195354.     

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.     

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.     

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).     

Zr 5Ir 2In 4 – A Superstructure of the Lu 5Ni 2In 4 Type

Zr₅Ir₂In₄ was synthesized by reaction of the elements in a glassy carbon crucible in a water-cooled sample chamber of an induction furnace. The sample was characterized by X-ray diffraction on both powder and single crystals. Zr₅Ir₂In₄ crystallizes with a pronounced Lu₅Ni₂In₄ type subcell, space group Pbam, a=1739.5(6), b=766.3(2), c=338.9(2) pm. Weak additional reflections force a doubling of the subcell c axis. The superstructure of Zr₅Ir₂In₄ is of a new type: Pnma, a=1739.5(6), b=677.8(2), c=766.3(2) pm, wR2=0.0529, 1592 F² values, and 60 variable parameters. The group-subgroup scheme for the klassengleiche symmetry reduction is presented. The formation of the superstructure is most likely due to a puckering effect (size of the iridium atoms). The crystal chemistry of Zr₅Ir₂In₄ is briefly discussed.     

Synthesis,structure characterization and thermal properties of [Zr6(μ3-O)4(μ3-OH)4(OOCCH2Bu)9(μ2-OH)3]2

Oxo/hydoxo zirconium(IV) complex of the general formula [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉(μ₂-OH)₃]₂ has been isolated, when Zr(OⁱPr)₄ reacted with a 2-fold excess of 3,3-dimethylbutyric acid. Single crystal X-ray diffraction data, collected at 103 and 153 K, showed that the studied compound crystallizes in hexagonal system (P6₃/m (no. 176)). Structure consists of dimers composed of [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉] sub-units, linked by six μ₂-OH bridges. Infrared spectroscopic studies proved the presence of hydroxo groups in the structure of studied clusters and formation of different types of oxo/hydroxo bridges. The application of variable temperature infrared spectroscopy and differential scanning calorimetry revealed that the structure of this complex undergoes the phase transitions at 143–183 and 203–293 K. Comparison of spectral and crystallographic data suggests that these phase transitions might be related to changes in the strength of Zr–O bonds of μ₂-OH bridges linking complex sub-units, and change in symmetry of the crystal lattice (from hexagonal to trigonal). Analysis of thermogravimetric data showed that decomposition of [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉(μ₂-OH)₃]₂ proceeds with complete conversion to ZrO₂ (monoclinic form) between 603 and 803 K.     

Synthesis and crystal structure of new one-dimensional copper(II) complex [Cu4(En)2(μ1,1-N3)4(μ1,1,1-N3)2(μ1,3-N3)2]n

A new polymer azido-bridged copper(II) complex [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂] _n (I) (En = ethylenediamine) has been synthesized and crystallography characterized. Complex I shows one-dimensional coordination polymeric structure based on a tetranuclear cluster unit [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂], in which the azido ions display three different bridging modes.     

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.     

Oxo Peroxo Glycolato Complexesof Vanadium (V). Crystal Structureof (NBu4)2[V2O2(O2)2(C2H2O3)2]?H2O

 Oxo peroxo glycolato complexes of vanadium(V) (M ₂[V₂O₂(O₂)₂(C₂H₂O₃)₂]ċnH₂O (n=0, 1; M=NBu₄ ⁺ (1), K⁺ (2), NH₄ ⁺ (3), Cs⁺ (4), NPr₄ ⁺ (5)) as well as (NBu₄)₂[V₂O₄(C₂H₂O₃)₂]ċ H₂O (6) have been prepared and characterized by spectroscopic methods. X-Ray structure analysis of 1 revealed the presence of dinuclear [V₂O₂(O₂)₂(C₂H₂O₃)₂]²⁻ anions with a (chemical structure) bridging core and six coordinated vanadium(V) atoms in a distorted pentagonal pyramidal array.     

Formation of the silylene-bridged complex Fe2(CO)6(μ2-SiCl2)3 from cis-Fe(CO)4(SiCl3)2: an experimental and computational study

Abstract  

Thermolysis of cis-Fe(CO)₄(SiCl₃)₂ results in the formation of the novel compound Fe₂(CO)₆(μ₂-SiCl₂)₃, which was characterized by single crystal X-ray diffraction. Density functional theory calculations were carried out to elucidate possible reaction steps leading to the formation of Fe₂(CO)₆(SiCl₂)₃, including CO dissociation and chlorine abstraction by a SiCl₃ radical generated from homolytic Fe–Si bond cleavage involving a singlet–triplet intersystem crossing.