Molecular Structures of Sulfur Cyanide Trifluoride, SF(3)CN, and Sulfinyl Cyanide Fluoride, FS(O)CN

General valence force fields for SF(3)CN and FS(O)CN are derived from vibrational data taken from the literature and from theoretical calculations. Gas phase electron diffraction studies on both molecules yield the following geometric parameters (r(a) distances and angles with 3sigma uncertainties). SF(3)CN: r(S-F(e)) = 155.2(4) r(S-F(a)) = 165.7(3), r(S-C) = 173.6(8), r(C&tbd1;N) = 115.9(4) pm; angle(F(a)SF(e)) = 86.9(3), angle(F(a)SC) = 86.0(4) angle(F(e)SC) = 98.7(8), angle(F(a)SF(a)) = 169.0(6), angle(SCN) = 171(4) degrees. FS(O)CN: r(S-F) = 159.8(3), r(S=O) = 143.2(2), r(S-C) = 178.3(3), r(C&tbd1;N) = 115.0(3) pm; angle(FSO) = 104.9(4), angle(FSC) = 93.9(4), angle(CSO) = 105.3(5), angle(SCN) = 176(4) degrees. These experimental results are compared to ab initio values (HF/3-21G, HF/6-31G, and MP2/6-31G), and the bonding properties in these sulfur (IV) cyanides are discussed.     

ChemInform Abstract: Matrix Reactions of Sulfur Atoms and Fluorine. IR Spectra of SF,SF2, and SF3 in Solid Argon.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

An infrared and raman spectroscopic study of metal(II) Di(2-methylpyridine) tetracyanonickelate complexes: Ni(C6H7N)2Ni(CN)4 and Cd(C6H7N)2Ni(CN)4

The results of an infrared and Raman spectroscopic study are reported for two new metal 2-methylpyridine tetracyanonickelate complexes, M(C₆H₇N)₂Ni(CN)₄, M=Ni or Cd. Their structure consists of corrugated polymeric layers of {M-Ni(CN)₄} with 2-methylpyridine molecules bound directly to the metal (M). These complexes can act as host lattices in the formation of inclusion compounds with dioxane guest molecules.     

Synthesis,Crystal Structure,and Characterization of A New Adduct Bis-(2-Amino-3-Benzyloxypyridinium) Selenate Monohydrate [C12H13N2O]2SeO4.H2O

Abstract

A new adduct bis-(2-amino-3-benzyloxypyridinium) selenate monohydrate, [C₁₂H₁₃N₂O]₂SeO₄.H₂O, has been synthesized by slow evaporation at room temperature using 2-amino-3-benzyloxypyridine as the structure-directing agent. The structure, determined by single-crystal X-ray diffraction at 298 K, can be described as organic-inorganic tunnels with different forms built by infinite inorganic chains parallel to the c axis and connected to the organic cations. In this atomic arrangement, hydrogen bonds and van der Waals interactions between the different species play an important role in the tri-dimensional network cohesion. Solid-state ¹³C and ⁷⁷Se MAS NMR spectroscopy results are in agreement with the X-ray structure.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures and tables.]     

氰根桥连的异金属配位聚合物{[Ni(pn)2][Fe(CN)4(bipy)]}2·3H2O(pn=1,3-丙二胺,bipy=2,2′-联吡啶)的合成与结构

以[Fe(CN)₄(bipy)]^2-为建筑块和[Ni(pn)₂]²⁺在水溶液中反应,合成了{[Ni(pn)₂][Fe(CN)₄(bipy)]}₂·3H₂O(pn=1,3-丙二胺)。通过X-射线单晶衍射确定了其晶体结构。该配合物属单斜晶系,P2₁/n空间群,晶胞参数为:a     

Synthesis and spectroscopic characterization of trinuclear [Ru3O(O2CCH3)6(pyrazine)3]0, + clusters

Summary [Ru₃O(O₂CCH₃)₆(pyrazine)₃]^{0, +} clusters have been synthesized and characterized based on electronic, infrared and resonance Raman spectra. Selective enhancement of the pyrazine and Ru₃O(O₂CCH₃)₆ vibrational modes has been observed in the case of the reduced cluster using excitation wavelengths close to the metal-to-pyrazine and metal-metal charge transfer band in the visible region.

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Synthese und spektroskopische Charakterisierung von dreikernigen [Ru₃O(O₂CCH₃)₆(Pyrazin)₃]^{0, +}-Clustern

Zusammenfassung Es wurden [Ru₃O(O₂CCH₃)₆(Pyrazin)₃]^{0, +}-Cluster dargestellt und mittels Elektronen-, Infrarot- und Resonanz-Raman-Spektren charakterisiert. Im Fall der reduzierten Cluster wurde bei Anregungswellenlängen nahe den Metall-Pyrazin- und Metall-Metall-Charge-Transfer-Banden im sichtbaren Bereich eine selektive Anhebung der Pyrazin- und Ru₃O(O₂CCH₃)₆-Vibrationen beobachtet.

     

新型氰基桥联配位聚合物[Ni(en)2]2[Ni(CN)4]2·5H2O的合成、晶体结构和磁性质

分子组装在材料科学、催化和生物化学中具有潜在的应用前景,所以分子组装引起了化学、固体物理学和生物学等领域科学家们的普遍关注犤1犦。分子组装常用的方法是使用具有配位能力的金属配合物作为建筑块与过渡金属阳离子反应。氰基桥联多核配合物由于其结构的多样性和具有特别优异的磁性质,近10年来在配位化学领域倍受关注犤2～8犦。在系列配合物犤M(en)2犦犤Ni(CN)4犦(M=Ni,Cu,Zn,Cd等)中,犤Cu(en)2犦犤Ni(CN)4犦和犤Cd(en)2犦犤Ni(CN)4犦的晶体结构已经通过单晶衍射的方法测得犤9,10犦。在犤Cu(en)2犦犤Ni(CN)4犦中,Cu原子为六配…     

Gas-phase chemistry of nitrogen trifluoride NF3: structure and stability of its M–NF3 (M=H, Li, Na, K) complexes

The stationary points characterizing the potential energy profiles of the complex processes of the M⁺(M=H, Li, Na, K) and NF₃ were investigated by QCISD and B3LYP in conjunction with the 6-311+G(2d,2p) basis set. The optimized geometries and NBO analysis indicate that the complexes of M⁺(M=Li, Na, K) and NF₃ exist as ion-dipole molecules. But for H⁺ complexes, there are two stable isomers NF₃H⁺ and NF₂⁺–HF. The interaction distances of isomers follow the sequence H⁺< Li⁺< Na⁺< K⁺. The calculated affinity energies of the most stable isomers of H⁺, Li⁺, Na⁺, and K⁺ complexes exceed 20.1 kJ/mol, and these values suggest that the M⁺–NF₃ (M=H, Li, Na, K) complexes could be observed as stable species in gas phase, which supports Fujii's proposal that Li⁺ ion attachment mass spectrometry can serve as a conceivable technique to quantify the emissions of the NF₃.     

2-(3-羟基-2-吡啶基)-苯并咪唑的合成、晶体结构及光谱研究

在合成2-(3-羟基-2-吡啶基)-苯并咪唑的基础上, 利用NMR (1H, 13C, COSY, HSQC 和HMBC), MS, IR 和UV 进
行了详细表征; 通过X-ray 单晶衍射测定该化合物的晶体结构, 实验结果表明该晶体属于单斜晶系{空间群为P21/c,
a＝14.289(3) Å, b＝10.618(2) Å, c＝12.783(3) Å, β＝93.51(3)°, V＝1935.8(7) Å3, Z＝8}, 很好支持了波谱表征的结果.
2-(3-羟基-2-吡啶基)-苯并咪唑的荧光光谱表明, 该化合物在激发态下存在双质子转移现象, 密度泛函计算结果合理解
释了实验现象.     

An infrared and Raman spectroscopic study of the Hofmann-type complexes and clathrates: M(piperidine)2Ni(CN)4; M(piperidine)2Ni(CN)4·1.5G (M=Cd, Co, Ni or Cu; G=benzene)

New Hofmann-type complexes and clathrates of the forms M(piperidine)₂Ni(CN)₄ and M(piperidine)₂Ni(CN)₄·1.5G (M=Cd, Co, Ni or Cu; G=benzene) were prepared in powder form and their infrared and Raman spectra are reported. The spectral features suggest that these compounds are similar in structure to the Hofmann-type clathrates except for the copper compounds. The complex and clathrate of Cu have different spectral features in comparison with its analogues due to the Jahn-Teller effect.     

Stabilization of Highly Reactive “Naked Anions”: Synthesis,Crystal Structure and Vibrational Spectrum of [Na(12‐crown‐4)2]2 [P2S6] · CH3CN

The novel thiodiphosphate, [Na(12‐crown‐4)₂]₂[P₂S₆] · CH₃CN, bis[di(12‐crown‐4)sodium] hexathiodiphosphate(V) acetonitrile solvate ( 1 ) has been synthesized by the reaction of Na₂[P₂S₆] with 12‐crown‐4 in dry acetonitrile. The title compound crystallizes in the tetragonal space group P4₂/mbc (no. 135), with a = 15.184(1) Å, c = 21.406(2) Å and Z = 4 and final R1 = 0.0671 and wR2 = 0.0809. The crystal structure is characterized by discrete sodium‐bound crown‐ether sandwich cations, [Na(12‐crown‐4)₂]⁺ and [P₂S₆]^2? ions with D_2h symmetry. Sodium ion is coordinated by the eight oxygen atoms of two crown‐ether molecules to form a square antiprisma. Solvent molecules of CH₃CN are statistically disordered. Distances and angles of the [P₂S₆]^2? unit are similar to those in [K(18‐crown‐6)]₂ [P₂S₆] · 2 CH₃CN, and in K₂[P₂S₆] and Cs₂[P₂S₆]. The FT‐Raman and FT‐IR spectrum of the title compound has been recorded and interpreted, especially with respect to the P₂S₆ group and in comparison to the few known metal hexathiodiphosphates(V).     

Synthesis and Crystal Structure of a Sandwiched Trinuclear Complex [Tl_2(18-Crown-6)_2Pt(CN)_4]·2H_2O

1 INTRODUCTION Tetracyanoplatinate ion often forms one-dimen- sional chain compounds, and the Pt–Pt spacings are often only 0.01~0.3 ? longer than those in Pt metal (2.78 ?). The studies of room-temperature electrical conductivities of these complexes indicate that the shorter the Pt–Pt separations in the chains are, the higher the electrical conductivity is[1~3]. Tetracyano- platinate ion may also stack with suitable planar cations into one-dimensional materials such as [Pt- (CNR)4]…     

Crystal Structures and Raman Spectra of cis‐[SnCl4(H2O)2]·2H2O,cis‐[SnCl4(H2O)2]·3H2O, [Sn2Cl6(OH)2(H2O)2]·4H2O,and [HL][SnCl5(H2O)]·2.5H2O (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime,C18H18N4O2)

The complexes cis‐[SnCl₄(H₂O)₂]·2H₂O ( 1 ), [Sn₂Cl₆(OH)₂(H₂O)₂]·4H₂O ( 3 ), and [HL][SnCl₅(H₂O)]·2.5H₂O ( 4 ) were isolated from a CH₂Cl₂ solution of equimolar amounts of SnCl₄ and the ligand L (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime, C₁₈H₁₈N₄O₂) in the presence of moisture. 1 crystallizes in the monoclinic space group Cc with a = 2402.5(1) pm, b = 672.80(4) pm, c = 1162.93(6) pm, β = 93.787(6)° and Z = 8. 4 was found to crystallize monoclinic in the space group P2₁, with lattice parameters a = 967.38(5) pm, b = 1101.03(6) pm, c = 1258.11(6) pm, β = 98.826(6)° and Z = 2. The cell data for the reinvestigated structures are: [SnCl₄(H₂O)₂]·3H₂O ( 2 ): a = 1227.0(2) pm, b = 994.8(1) pm, c = 864.0(1) pm, β = 103.86(1)°, with space group C2/c and Z = 4; 3 : a = 961.54(16) pm, b = 646.29(7) pm, c = 1248.25(20) pm, β = 92.75(1)°, space group P2₁/c and Z = 4.     

Synthesis,spectroscopic characterization,and X-ray crystal structure of tris(trimethylsilyl)cyanurate

Tris(trimethylsilyl)cyanurate, C₁₂H₂₇N₃O₃Si₃ (1), has been synthesized and characterized by elemental analysis, IR, Raman, ¹³C and ²⁹Si NMR, and thermogravimetric methods. The molecular and crystal structure has been determined by single crystal X-ray diffraction. This compound crystallized in space group P6₃/m (176), Z = 2 with a = 11.017(2), b = 11.017(2), c = 9.676(3) Å; α = 90°, β = 90°, γ = 120°. The geometry of the molecule is compared with tris(trimethylsilyl)cyamelurate.     

Complexations of Hg(CN)(2) with imidazolidine-2-thione and its derivatives: solid state, solution NMR and antimicrobial activity studies

The preparation and characterization of new mercuric complexes of formula L(2)Hg(CN)(2) with L being imidazolidine-2-thione (Imt) and its substituted derivatives, 1,3-diazinane-2-thione (Diaz), 1,3-diazipane-2-thione (Diap), are described. The solution and solid-state (13)C NMR show a significant shift of the CS carbon resonance of the ligands, while the other resonances are relatively unaffected, indicating that most likely the solid-state structure is maintained in solution as well. The principal components of the (199)Hg shielding tensors were determined from solid-state NMR data. Antimicrobial activity studies of the free ligands and their complexes show that ligands exhibit substantial antibacterial activities compare to their Hg(II) complexes.     

Methanesulfenyl fluoride, CH3SF, a missing link in the family of sulfenyl halides: formation and characterization through the matrix photochemistry of methyl thiofluoroformate, FC(O)SCH3

Matrix-isolation experiments have afforded the means of preparing the hitherto unknown sulfur(II) fluoride, methanesulfenyl fluoride, CH3SF. Broadband UV-visible irradiation of methyl thiofluoroformate, FC(O)SCH3, isolated in a solid Ar matrix results, first, in photoisomerization of the syn into the anti form of the molecule, and, subsequently, in the elimination of CO with the concomitant formation of CH3SF. Continued irradiation brings about tautomerization of this product with the detachment and migration of a hydrogen from the methyl group to give the molecular complex H2C==S...HF. The changes have been monitored and the photoproducts detected and identified by the IR spectra of the matrices, and the conclusions confirmed: 1) with reference to the corresponding behavior of the perdeuterated molecule FC(O)SCD3; 2) by analogy with the properties of related molecules, for example, ClC(O)SCH3, CH3SCl, and H2C==S...HCl, and; 3) by comparison with the vibrational properties simulated for the different molecules by ab initio and density functional theory methods.