The Influence of the Counterions [AsF6]– and [GeF6]2– on the Structure of the [ClSO2NH3]+ Cation

Chlorosulfonamide reacts in the superacidic solutions HF/GeF₄ and HF/AsF₅ under the formation of ([ClSO₂NH₃]⁺)₂[GeF₆]^2– and [ClSO₂NH₃]⁺[AsF₆]^–, respectively. The chlorosulfonammonium salts were characterized by X‐ray single crystal structure analysis as well as vibrational spectroscopy and discussed together with quantum chemical calculations. ([ClSO₂NH₃]⁺)₂[GeF₆]^2– crystallizes in the triclinic space group P1 with one formula unit in the unit cell. [ClSO₂NH₃]⁺[AsF₆]^– crystallizes in the monoclinic space group P2₁/n with four formula units in the unit cell. Dependent on the counterion, [AsF₆]^– or [GeF₆]^2–, considerable structural differences of the [ClSO₂NH₃]⁺ cation are observed. Furthermore, the hitherto unknown X‐ray single crystal structure of chlorosulfonamide is determined in the course of this study. Chlorosulfonamide crystallizes in the orthorhombic space group Pmc2 with four formula units per unit cell.     

Crystal Structure and Vibrational Spectra of ClSO2NHC(O)F

The reaction of chlorosulfonyl isocyanate (ClSO₂NCO) with anhydrous hydrogen fluoride (aHF) leads to the formation of ClSO₂NHC(O)F. The title compound with a melting point of –38 °C is characterized by vibrational spectroscopy and a single crystal structure analysis. It crystallizes in the tetragonal space group I4₁/a with 16 formula units per unit cell. a = 11.1115(2) Å, c = 16.5654(6) Å. The experimental data are supported by quantum‐chemical calculations on the PBE1PBE/6‐311G(3pd,3df) level of theory.     

单次碰撞条件下Ar(3P0.2)与SO2,SOCl2的传能反应

利用化学发光方法研究了Ar（3P0,2）与SO2，SOCl2在单次碰撞条件下SO（A）的形成动力学，通过对实验光谱进行曲线拟会，得到了SO（A，υ＇）的初生态布居．分别是N0：N1：N2：N3：N4：N5：N6＝1．00：0．67：0．57：0．55：0．50：0．35：0．30和1．00：0．69：0．61：0．53：0．40：0．34：0．26．利用参考反应法求算了SO（A）的形成速率，分别为：4．55×10－12cm3•molecule－1•s－1和2．87×10－12cm3•molecule－1•s－1，与总猝灭速率相比较，发现解离激发为反应的次要出口通道．通过惊奇度分析，对激发解离机理进行了讨论．     

键长、价层轨道能与A─H键振动频率

键长、价层轨道能与Ａ─Ｈ键振动频率喻典，吕祖美（重庆师范学院重庆６３００４７）（重庆沙坪坝区教师进修学校重庆６３００００）关键词：氢化物，振动频率，价层轨道平均能键长振动频率的大小反映了化学键的强弱和分子的稳定性，由于测定的实验数据有限，建立简单而准...     

1,2-二硒-3，4-二硫方酸的从头计算

在RHF／STO－3G、STO－3G和3－21G（仅对ZE型）水平上，用abinitioSCF方法优化得到1，2－二硒－3，4－二硫方酸（3，4－二巯基－3－环丁烯－1，2－二硒酮）三种平面异构体的平衡构型，进一步用3－21G／／STO－3G（对ZZ和EE型）方法计算总能量，发现三种平面导构体中ZZ型是最稳定构象，ZE型次之，并与1，2－二硒方酸和3，4－二硫方酸从头算结果作了比较，用abinitio数值方法在STO－3G水平上计算了三种异构体的谐振动频率．     

Theoretical study of structures, energetics and vibrational properties of BC H species

Theoretical study using self-consistent field (SCF), hybrid density functional theory (B3LYP) and quadratic configuration interaction including single and double excitations (QCISD) with the Dunning correlation consistent polarized valence double zeta (cc-pVDZ) basis set have been used to examine the structures and vibrational properties of the singlet species with BC H stoichiometry. Relative stabilities are estimated at the CCSD(T)/cc-pVTZ level using QCISD/cc-pVDZ optimized geometries. Five species corresponding to different nuclear arrangements have been studied. The absolute minimum corresponds to the 2 aromatic borirene molecule (HBC H with a BC ring). Ethynylborane (H BCCH, C ) and borallene (H CCBH, C ) are respectively 6.4 and 24.3 kcal/mol higher. Vinylborine (C H B, C ) and H CBCH (C ) are much less stable, 46.2 and 49.1 kcal/mol respectively higher than borirene. The calculated vibrational spectra agree with experiment and confirm the infrared matrix characterization of the three most stable species.     

The low frequency IR and Raman spectra of some complexes of dithiooxamide with cadmium halides

summary The low frequency IR and Raman spectra of Cd(DH ₄)X ₂ (X=Cl, Br;DH=dithiooxamide) have been discussed. On the basis of the cadmium isotope and H-D shift as well as chlorine-bromine substitution a band assignment in the region 500–33 cm^–1 has been made. A polymeric structure of Cd(DH ₄)X ₂ involving both dithiooxamide and halogen bridges with D_4h symmetry of the cadmium environment is assumed.

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Die niederfrequenten IR- und Raman-Spektren einiger Komplexe von Dithiooxamid mit Cadmiumhalogeniden

Zusammenfassung Die IR- und Raman-Spektren von Cd(DH ₄)X ₂ (X=Cl, Br;DH=Dithiooxamid) werden im Bereich niedriger Frequenzen diskutiert. Basierend auf Cadmiumisotopen- und H-D-Verschiebungen mit zusätzlicher Cl-Br-Substitution werden die Banden im Bereich von 500–33 cm^–1 zugeordnet. Es wird eine polymere Struktur von Cd(DH ₄)X ₂ unter Anteilnahme sowohl von Dithioxamid- als auch Halogenbrücken mit einer D_4h-Symmetrie im Bereich des Cadmiumzentralions angenommen.

     

Kristallstruktur,Schwingungsspektren und Normalkoordinatenanalyse von K2[IrCl5(NH3)]

Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of K₂[IrCl₅(NH₃)] The X-ray structure determination of K₂[IrCl₅(NH₃)] (orthorhombic, space group Pnma, a = 13.426(4), b = 10.015(2), c = 6.8717(7) Å, Z = 4) revealed the C_s point symmetry of the complex anion [IrCl₅(NH₃)]^2? (Ir? Cl = 2.337–2.365, Ir? N = 2.067(10); N? H = 0.73–0.79 Å). Using the molecular parameters the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(NH) = 5.88, f_d(IrN) = 2.66, f_d(IrCl) = 1.68 mdyn/Å.     

Synthesis and spectral and structural characterization of a bridging chloropicolinatocopper(II) complex,Cu(C5H4NCOO)Cl

Summary The title complex of copper(II) chloride with picolinic acid was prepared and characterized by spectroscopic and X-ray crystallographic methods. The complex, Cu(C₅H₄NCOO)Cl, crystallizes tetragonal, space group P4₂/n (No. 86),a=976.4(1),c=1499.6(4) pm,N=8;R _w=0.048 for 543 observed MoK diffractometer data. In the structure of the complex two -chloro bridges form only slightly bent Cu₂Cl₂ rings [Cu-Cl=224.2(4) and 275.6(4) pm] with Cu...Cu separation of 359.4(2) pm and Cl...Cl separation of 348.7(5) pm. These edge-sharing copper coordination polyhedra are further linked via the N and O donor atoms of the picolinato anions at Cu-N distances of 199.6(12) pm and Cu-O bond lengths of 195.7(8) and 200.6(10) pm, to form a two-dimensional layer structure in which these layers are arranged along theab plane. Each picolinate anion functions as a tetra-dentate ligand: N(1) and O(2) are coordinated to the same Cu(II) center whereas O(1) is bonded to a neighbouring Cu(II) center. O(2) is further bonded to the latter Cu(II) center at a long Cu-O distance of 256.5(8) pm. The electronic, infrared and Raman spectra of the solid complex are reported and discussed.

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Synthese und spektroskopische und strukturelle Charakterisierung eines verbrückten Chloropicolinatokupfer(II) Komplexes, Cu(C₅H₄NCOO)Cl

Zusammenfassung Der Titelkomplex aus Kupfer(II)chlorid und Picolinsäure wurde dargestellt und mit spektroskopischen und Röntgen-Einkristall-Methoden charakterisiert. Cu(C₅H₄NCOO)Cl kristallisiert tetragonal, Raumgruppe P4₂/n (No. 86),a=976.4(1),c=1499.6(4) pm,N=8;R _w=0.048 für 543 beobachtete Mok-Diffraktometerdaten. In der Kristallstruktur bilden zwei -chloro-Brücken nur wenig gewinkelte Cu₂Cl₂-Ringe aus [Cu-Cl=224.2(4) und 275.6(4) pm], mit Cu...Cu Abständen von 359.4(2) pm und Cl...Cl Abständen von 348.7(5) pm. Die kantenverknüpften Koordinationspolyeder der Kupferatome sind in Richtung derab-Ebene über die N- und O-Donoratome der Picolinat-Anionen [mit Cu-N Abständen von 199.6(12) pm und Cu-O Abständen von 195.7(8) und 200.6(10) pm] zu einer zweidimensionalen Schichtstruktur verknüpft. Jedes Picolinat-Anion fungiert als vierzähniger Ligand: N(1) und O(2) sind zum selben Cu(II)-Zentrum gebunden; O(1) ist zum benachbarten Cu(II)-Zentrum koordiniert, zu dem O(2) einen langen Cu-O-Abstand von 256.5(8) pm ausbildet. Die elektronischen, Infrarot- und Raman-Spektren des Festkörper-Komplexes werden berichtet und diskutiert.

     

A multiconfigurational SCF computational method for the resolution of the vibrational Schrödinger equation in polyatomic molecules

Summary A new variational method for solving the molecular vibration problem is proposed. The so-called VMCSCF method (vibrational multiconfigurational self-consistent field) is based on the super-CI algorithm, previously developed in the framework of electronicab initio calculations. This approach makes direct use of the generalised Brillouin theorem to ensure self-consistency. The method is dedicated to the study of strongly interacting states (vibrational resonances), which are one of the main sources of perturbation in vibrational spectra. The interest of the method to tackle resonance interactions is illustrated by means of test calculations performed on the water and formaldehyde molecules.