新型层状异金属配位聚合物{[(CuL)2Sr(H2O)·Sr2(H2O)7]·2H2O·0.5CH3OH}n的合成、表征及晶体结构

合成了铜锶异金属配位聚合物,并通过元素分析和IR光谱对其进行了表征,利用X射线单晶衍射测定了其晶体结构.该化合物为具有{[(CuL)2Sr(H2O).Sr2(H2O)7].2H2O.0.5CH3OH}n化学组成的二维层状配位聚合物[H4L=N-(3-羧基水杨醛)-N′-(2-羟基苯甲酰基)乙撑二胺],其结构单元由两个相邻的片段组成,这些结构单元彼此相互配位,从而形成了一种结构新颖的层状配位聚合物.     

Crystal structure of one of the strontium hydroacetates,Sr(H2O)2(CH3COO)2[H2(CH3COO)3]

All-Union Scientific-Research Institute for Chemical Reagents and Ultrapure Chemical Substances. Translated from Zhurnal Strukturnoi Khimii, Vol. 29, No. 1, pp. 104–108, January–February, 1988.     

Calcium and strontium thio­sulfate,CaS2O3·6H2O and SrS2O3·5H2O

In contrast to former morphological studies, the results presented here show that calcium(II) thio­sulfate hexahydrate, CaS₂O₃·6H₂O, crystallizes centrosymmetrically in the pinacoidal class (point group ). The structure is characterized by chains, parallel to [100], of alternating S₂O₃ and Ca(H₂O)₆O₂ groups sharing common O atoms. The composition of each chain link is [Ca(H₂O)₆(S₂O₃)]. The geometry is analysed and compared in detail with the structural features of monoclinic strontium(II) thio­sulfate pentahydrate, SrS₂O₃·5H₂O, which forms layers, parallel to (100), of alternating S₂O₃ and Sr(H₂O)₄O₅ groups connected via common O atoms and O–O edges. Each layer contains [Sr(H₂O)₃O(S₂O₃)]_∞ as the unique repeat unit.     

Kristallstrukturen des Sr(OH)2 · H2O,Ba(OH)2 · H2O (o.-rh. und mon.) und Ba(OH)2 · 3 H2O

Crystal Structures of Sr(OH)₂ · H₂O, Ba(OH)₂ · H₂O (o.-rh. and mon.), and Ba(OH)₂ · 3 H₂O The crystal structures of Ba(OH)₂ · 3 H₂O (Pnma, Z = 4), γ-Ba(OH)₂ · H₂O (P2₁/m, Z = 2) and the isotypic Sr(OH)₂ · H₂O and β-Ba(OH)₂ · H₂O (Pmc2₁, Z = 2) were determined using X-ray single crystal data. Ba(OH)₂ · 3 H₂O and Ba(OH)₂ · H₂O mon. crystallize in hitherto unknown structure types. The structure of Ba(OH)₂ · H₂O mon. is strongly related to that of rare earth hydroxides M(OH)₃ with space group P6₃/m (super group of P2₁/m). The metal-oxygen distances are significantly shorter for OH^? ions (mean Ba—O bond lengths of all hydroxides under investigation 278.1 pm) than for H₂O molecules (289.9 pm). Corresponding to other hydrates of ionic hydroxides, the water molecules form strong hydrogen bonds to adjacent OH^? ions whereas the hydroxide are not H-bonded.     

OH stretch IR spectra of (H2O)3 and benzene-(H2O)3

The OH stretch IR spectrum of (H₂O)₃ is significantly altered upon complexation of the cluster with a benzene molecule. Theoretical calculations show that the differences in the OH stretch spectra of (H₂O)₃ and benzene-(H₂O)₃ are primarily due to mode localization induced by the benzene molecule. Received: 27 January 1997 / Accepted: 28 January 1997     

Herstellung und Eigenschaften der Verbindungen Sr2(MnO4)OH und Sr2(MnO4)OH·2H2O

Zusammenfassung Es wird die Herstellung der Verbindungen Sr₂(MnO₄)OH und Sr₂(MnO₄)OH·2H₂O beschrieben. Die Gitterkonstanten wurden aus den entsprechenden Pulverdiagrammen berechnet. Die Infrarotabsorptions-und die Reflexionsspektren im Sichtbaren sowie das magnetische und thermische Verhalten wurden untersucht und kurz besprochen.

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Preparation and properties of the compounds Sr₂(MnO₄)OH and Sr₂(MnO₄)OH·2H₂O

Methods for preparation of the anhydrous compound formulated as Sr₂(MnO₄)OH and of its dihydrate are described. Unit cell parameters, which are the same for both substances, have been calculated from X-ray powder diagramms. Infrared absorption and visible reflectance spectra as well as the magnetic and thermal properties are also reported and briefly discussed.

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Mit 4 Abbildung     

Products of the gas-phase reactions of OH radicals with (C2H5O)2P(S)CH3 and (C2H5O)3PS

Products of the gas-phase reactions of OH radicals with O,O-diethyl methylphosphonothioate [(C2H5O)2P(S)CH3, DEMPT] and O,O,O-triethyl phosphorothioate [(C2H5O)3PS, TEPT] have been investigated at room temperature and atmospheric pressure of air using in situ atmospheric pressure ionization mass spectrometry (API-MS) and, for the TEPT reaction, gas chromatography and in situ Fourier transform infrared (FT-IR) spectroscopy. Combined with products quantified previously by gas chromatography, the products observed were: from the DEMPT reaction, (C2H5O)2P(O)CH3 (21+/-4% yield) and C2H5OP(S)(CH3)OH or C2H5OP(O)(CH3)SH (presumed to be C2H5OP(O)(CH3)SH by analogy with the TEPT reaction); and from the TEPT reaction, (C2H5O)3PO (54-62% yield), SO2 (67+/-10% yield), CH3CHO (22-40% yield) and, tentatively, (C2H5O)2P(O)SH. The FT-IR analyses showed that the formation yields of HCHO, CO, CO2, peroxyacetyl nitrate [CH3C(O)OONO2], organic nitrates, and acetates from the TEPT reaction were <5%, 3+/-1%, <7%, <2%, 5+/-3%, and 3+/-2%, respectively. Possible reaction mechanisms are discussed.     

Cation-cation interactions in Sr5(UO2)20(UO6)2O16(OH)6(H2O)6 and Cs(UO2)9U3O16(OH)5

Two novel U6+ compounds, Sr5(UO2)20(UO6)2O16(OH)6(H2O)6 (SrFm) and Cs(UO2)9U3O16(OH)5 (CsFm), have been synthesized by mild hydrothermal reactions. The structures of SrFm (orthorhombic, C2221, a = 11.668(1), b = 21.065 (3), c = 13.273 A, V = 3532.5(1) A3, Z = 2) and CsFm (trigonal, R3c, a = 11.395(2), c = 43.722(7) A, V = 4916.7(1) A3, Z = 6) are rare examples of uranyl compounds that contain cation-cation interactions where an O atom of one uranyl ion is directly linked to another uranyl ion. Both structures are complex frameworks. SrFm contains sheets of polyhedra that are linked through cation-cation interactions with uranyl ions located between the sheets. CsFm possesses an unusually complex framework of vertex- and edge-sharing U6+ polyhedra that incorporates cation-cation interactions.     

A new orthoborate,Sr3Ga3(BO3)4O(OH)

The crystal structure of tristrontium trigallium tetraborate oxide hydro­xide has been determined by X‐ray diffraction using a crystal grown by hydro­thermal crystallization of a strontium gallo‐borate glass. It represents a new orthoborate structure type built of complex layers formed by BO₃ triangles sharing corners with Ga₂O₇ tetrahedral dimers and GaO₄OH square pyramids. The Sr atoms occupy both inter‐ and intralayer sites.     

Many-body decomposition of the binding energies for OH.(H2O)2 and OH.(H2O)3 complexes

We use ab initio electronic structure methods to calculate the many-body decomposition of the binding energies of the OH.(H2O)n (n=2,3) complexes. We employ MP2 and CCSD(T) levels of theory with aug-cc-pVDZ and aug-cc-pVTZ basis sets and analyze the significance of the nonpairwise interactions between OH radical and the surrounding water molecules. We also evaluate the accuracy of our newly developed potential function, the modified Thole-type model, for predicting the many-body terms in these complexes. Our analysis of the many-body contributions to the OH.(H2O)n binding energies clearly shows that they are just as important in the OH interactions with water as they are for interactions in pure water systems.     

Adsorption of O, H, OH, and H2O on Ag(100)

The adsorption of H(2)O and its dissociation products, O, H, and OH, on Ag(100) has been studied using an ab initio embedding method. Results at different sites (atop, bridge, and hollow) are presented. The four-fold hollow site is found to be the most stable adsorption site for O, H, and OH, and the calculated adsorption energies are 87.1, 42.7, and 76.2 kcal mol(-1), respectively. The adsorption energy of water at the atop and bridge sites is almost identical with values of 11.1 and 12.0 kcal mol(-1), respectively. The formation of adsorbed OH species by adsorption of water on oxygen-precovered Ag(100) is predicted to be exothermic by 36 kcal mol(-1).     

Syntheses,Crystal Structures and Properties of Three New Complexes [Ni（C9N2O2H7）2（CH3OH）2],[Zn（C9N2O2H7）2（H2O）2] and [Cd（C9N2O2H7）2（CH3OH）2]

Three novel metal-organic complexes with formulas [Ni(C9N2O2H7)2(CH3OH)2](1),[Zn(C9N2O2H7)2(H2O)2](2) and [Cd(C9N2O2H7)2(CH3OH)2](3) were synthesized by the reactions of Ni,Zn and Cd salts with ethyl 2-benzimidazolylacetate under hydrothermal conditions or layering technique,and characterized by single-crystal X-ray diffraction analysis,IR spec-troscopy,solid-state luminescent properties and thermogravimetric(TG) analysis.The crystal data for these three complexes are as follows:for 1,monoclinic,space group P21/c,a = 9.384(3),b = 9.634(3),c = 11.292(3) ,β = 95.787(5)°,V = 1015.7(5) 3,Z = 2,F(000) = 492,Dc = 1.547 Kg/m3,μ = 1.002 mm-1,the final R = 0.0451 and wR = 0.0900 for 1833 observed reflections with Ⅰ 2σ(Ⅰ);for 2,orthorhombic,space group Pbca,a = 10.031(4),b = 10.379(4),c = 17.525(7),V = 1824.6(12) 3,Z = 4,F(000) = 928,Dc = 1.645 Kg/m3,μ = 1.392 mm-1,the final R = 0.0452 and wR = 0.0996 for 1661 observed reflections with Ⅰ 2σ(Ⅰ);for 3,monoclinic,space group P21/c,a = 9.9114(13),b =10.4852(15),c = 10.4120(14) ,β = 108.453(5)°,V = 1026.4(2) 3,Z = 2,F(000) = 532,Dc = 1.705 Kg/m3,μ = 1.110 mm-1,the final R = 0.0322 and wR = 0.0805 for 1822 observed reflections with Ⅰ 2σ(Ⅰ).In the three complexes,the ethyl 2-benzimidazolylacetate shows the same chelating mode,and the adjacent units are interlinked into a two-dimensional layer through hydrogen-bonds(O-H···O,N-H···O).