Binary group 15 polyazides. structural characterization of [Bi(N3)4]-, [Bi(N3)5]2-, [bipy·Bi(N3)5]2-, [Bi(N3)6]3-, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2 and on the lone pair activation of valence electrons

The binary group 15 polyazides As(N(3))(3), Sb(N(3))(3), and Bi(N(3))(3) were stabilized by either anion or donor-acceptor adduct formation. Crystal structures are reported for [Bi(N(3))(4)](-), [Bi(N(3))(5)](2-), [bipy·Bi(N(3))(5)](2-), [Bi(N(3))(6)](3-), bipy·As(N(3))(3), bipy·Sb(N(3))(3), and [(bipy)(2)·Bi(N(3))(3)](2). The lone valence electron pair on the central atom of these pnictogen(+III) compounds can be either sterically active or inactive. The [Bi(N(3))(5)](2-) anion possesses a sterically active lone pair and a monomeric pseudo-octahedral structure with a coordination number of 6, whereas its 2,2'-bipyridine adduct exhibits a pseudo-monocapped trigonal prismatic structure with CN 7 and a sterically inactive lone pair. Because of the high oxidizing power of Bi(+V), reactions aimed at Bi(N(3))(5) and [Bi(N(3))(6)](-) resulted in the reduction to bismuth(+III) compounds by [N(3)](-). The powder X-ray diffraction pattern of Bi(N(3))(3) was recorded at 298 K and is distinct from that calculated for Sb(N(3))(3) from its single-crystal data at 223 K. The [(bipy)(2)·Bi(N(3))(3)](2) adduct is dimeric and derived from two BiN(8) square antiprisms sharing an edge consisting of two μ(1,1)-bridging N(3) ligands and with bismuth having CN 8 and a sterically inactive lone pair. The novel bipy·As(N(3))(3) and bipy·Sb(N(3))(3) adducts are monomeric and isostructural and contain a sterically active lone pair on their central atom and a CN of 6. A systematic quantum chemical analysis of the structures of these polyazides suggests that the M06-2X density functional is well suited for the prediction of the steric activity of lone pairs in main-group chemistry. Furthermore, it was found that the solid-state structures can strongly differ from those of the free gas-phase species or those in solutions and that lone pairs that are sterically inactive in a chemical surrounding can become activated in the free isolated species.     

As-5、[As5M]-、[As5MAs5]2- (M=Ti,Zr, Hf)的结构和芳香性

用密度泛函理论(DFT)研究了As-5、[As5M]-和[As5MAs5]2- (M=Ti, Zr, Hf)的结构、频率、能量以及芳香性, 详细讨论了体系中不同类型的键和电子如化学键、孤对电子、核电子等对总的核独立化学位移(NICS)的影响. 结果表明, As-5、[As5M]-和[As5MAs5]2-的基态结构分别具有D5h、C5v和D5h对称性, 而且都具有芳香性. As-5 (D5h)的芳香性主要来源于As—As π键和As—As σ键的作用. [As5M]-(C5v)中各种As—M键的NICS分割值占主要优势, 其次是As—As之间形成的σ键. [As5TiAs5]2-(D5h)中, As—As π键的作用占主要优势. [As5ZrAs5]2-(D5h)中, As—As π键对体系总的NICS贡献相对减小, 而As—Zr键的作用增强. [As5HfAs5]2-(D5h)的芳香性主要来自As—Hf键的作用.     

Synthesis and structure of bismuth-containing complexes [Ph3PMe] 2 + [BiI5]2− and [Ph3PMe] 2 + [BiI5 · C5H5N]2− · C5H5N

The complexes [Ph₃PMe] ₂ ⁺ [BiI₅]^2? (I) and [Ph₃PMe] ₂ ⁺ [BiI₅ · C ₅H₅N]^2? · C ₅H₅N (II) were synthesized by the reaction of bismuth triiodide with triphenylmethylphosphonium iodide, and their structures were determined by X-ray diffraction analysis. The P atom in cation I has slightly distorted tetragonal coordination polyhedron (the CPC angles 109.42(4)° and 109.52(4)°, the bond lengths P-C_Ph 1.779(2), P-C_Me 1.793(1) Å. The Bi atom in the anion of complex I has an ideal trigonal-bipyramidal coordination polyhedron (Bi-I_eq 3.0031(4), Bi-I_eq 3.0485(5) Å). The crystal of complex II consists of the anions [BiI₅ · C ₅H₅N]^2?, solvated pyridine molecules, and two types of crystallographically independent tetrahedral triphenylmethylphosphonium cations (the angles CPC 106.9(1)°–111.7(1)°, the distances P-C_Ph 1.785(3)–1.792(3), P-C_Me 1.793(3), 1.786(3) Å). The Bi atoms in the anion of complex II have a distorted octahedral coordination polyhedron (Bi-I 3.0878(4)–3.1240(3), Bi-N(1) 2.628(3) Å).     

N，N’-二[3-氯-5S-（l-孟氧基）-2（5H）-4-呋喃酮基]-1，4-丁二胺的合成及晶体结构

合成了N,N’-二[3-氯-5S-（l-孟氧基）-2（5H）-4-呋喃酮基]-1,4-丁二胺,并通过IR,^1H NMR,MS和X射线单晶衍射对其进行了表征．X射线单晶衍射结果表明：标题化合物的不对称结构单元中包含一个平面的呋喃酮环和一个椅式的环己烷环,四个手性中心．标题化合物通过N—H…O分子间氢键作用实现空间堆积．     

Bi3GaS5]2[Ga3Cl10]2[GaCl4]2·S8 containing heterocubane-type [Bi3GaS5]2+, star-shaped [Ga3Cl10]-, monomeric [GaCl4]- and crown-like S8

By reaction of elemental bismuth, sulfur, bismuth(III) chloride and gallium(III) chloride in the ionic liquid (BMIm)Cl (BMIm: 1-butyl-3-methylimidazolium), [Bi(3)GaS(5)](2)[Ga(3)Cl(10)](2)[GaCl(4)](2)·S(8) is obtained as red transparent crystals. According to X-ray structure analysis based on single crystals, the title compound crystallizes with triclinic lattice symmetry and is composed of heterocubane-type [Bi(3)GaS(5)](2+) cations, trimeric star-shaped [Ga(3)Cl(10)](-) anions with three (GaCl(4)) tetrahedra sharing a single central chlorine atom, monomeric [GaCl(4)](-) tetrahedra and neutral, crown-shaped S(8)-rings. Here, the heterocubane [Bi(3)GaS(5)](2+) as well as the star-shaped [Ga(3)Cl(10)](-) are observed as building units for the first time. [Bi(3)GaS(5)](2)[Ga(3)Cl(10)](2)[GaCl(4)](2)·S(8) is further characterized by X-ray powder diffraction as well as by thermogravimetry/differential thermal analysis.     

N,N′-二[3-氯-5S-(l-孟氧基)-2(5H)-4-呋喃酮基]-1,4-丁二胺的合成及晶体结构(英文)

合成了N,N′-二[3-氯-5S-(l-孟氧基)-2(5H)-4-呋喃酮基]-1,4-丁二胺,并通过IR,1H NMR,MS和X射线单晶衍射对其进行了表征.X射线单晶衍射结果表明:标题化合物的不对称结构单元中包含一个平面的呋喃酮环和一个椅式的环己烷环,四个手性中心.标题化合物通过N—H…O分子间氢键作用实现空间堆积.     

影响合成檀香3-甲基-5-(2,2,3-三甲基环戊烯[3]基[1])戊醇[2]质量的因素分析

天然檀香是人们喜爱的一种高级香料。其香气甜润而富有传统的东方香型特色。由于天然檀香的产量少,价格昂贵,而且提炼天然檀香的檀香木来源日益减     

Synthesis and Crystal Structure of 2,2-Dimethyl-4-[1H-（ 1,2,4-triazolyl）]-4- [ 1H-benzotriazolyl]-3- butanone[t-BuCOCH（C2H2N3）（C6H4N3）]

1 INTRODUCTION Triazole nuclei appear frequently in the structures of various natural products and biologically active compounds, notably thiamine (vitamin B), peni- cillins, antibiotics such as micrococcin[1], and many metabolic products of fungi and p…     

1.3λ3-Azaphospholo[1.2-α]pyridine - 1.2.4.λ3-diazaphospholo[1.5-α]pyridine - 1.3λ3-azaarsolo[1.5-α]pyridine - 1.2.4λ3-diazaarsolo[1.5-α]pyridine

The title compounds are prepared by reaction of 1.3-oxazolo[13.2-α]pyridinium- and 1.3.4-oxadiazolo[3.2-α]pyridiniumsalts with P(SiMe₃)₃, resp. As(SiMe₃)₃.     

Crystal structure of the N,N′,N″-triphenyl-guanidinium-bis-[η5-π-(3)-dicarbollide]Ni(III) complex

Single crystals of a new compound containing triphenylguanidinium and bis(dicarbollide)nickel(III) [C(NHC₆H₅)₃][Ni(B₉C₂H₁₁)₂] are obtained and analyzed by LOW-TEMPERATURE. Crystallographic data are: C₂₃H₄₀B₁₈N₃Ni, M = 611.87, monoclinic system, space group P2₁/c, unit cell parameters: a = 21.9085(5) Å, b = 19.9294(4) Å, c = 14.8721(4) Å, β = 91.4033(9)°, V = 6491,5(4) ų, Z = 8, d _x = 1.252 g/cm³, T = 100 K, F(000) = 2536, μ = 0.621 mm^?1. The structure was solved by direct and Fourier methods and refined by the full matrix least squares technique in the anisotropic/isotropic (for H atoms) approximation up to the final factor R ₁ = 0.053 for 10429 I _hkl ≥ 2σ _I (Bruker X8 APEX diffractometer, {ie547-1} radiation). It contains two independent [C(NHC₆H₅)₃]⁺ cations with different conformations and two [Ni(B₉C₂H₁₁)₂]^? anions with the same transoid conformation. Three types of weak intermolecular interactions are found: {ie547-2}; C-H…π between the H(C) atoms of cluster anions and delocalized π systems of Ph rings of cations; π…π interactions of Ph rings of cation 2 with each other.     

Enthalpie- und entropiedifferenz der verbrückten und unverbrückten form des cyclopentadienylruthenium-dicarbonyl-dimeren, [RuC5H5(CO)2]2, sowie der analogen eisenverbindungen [FeC5H5(CO)2]2

The enthalpy and entropy differences for the equilibrium

has been determined in solution.With M = Ru one obtains ΔH = +1.56 kcal/Mol and ΔS = +5.5 cal/Mol·degree in CS₂ solution. At 30° 45% of (I) and 55% of (II) are in equilibrium. With M = Fe the approximate values are: ΔH 4 kcal/Mol and ΔS 3 cal/Mol·degree. At 30° about 0.6% of (II) are present in the equilibrium mixture in nonane solution.     

Catalyst-free glycerol-mediated green synthesis of 5′-thioxospiro[indoline-3,3′-[1,2,4]triazolidin]-2-ones/spiro[indoline-3,3′-[1,2,4]triazolidine]-2,5′-diones

The development of new catalyst-free green and efficient protocol to access 5′-thioxospiro[indoline-3,3′-[1,2,4]triazolidin]-2-ones/spiro[indoline-3,3′-[1,2,4]triazolidine]-2,5′-diones, potential privileged scaffolds for drug discovery, is disclosed. Key feature of this methodology is the dual use of glycerol—a recyclable, bioorganic compound, as a solvent cum promoter. Other highlights include use of inexpensive reagents, mild reaction conditions, operational simplicity, short reaction time, no need for chromatographic purification, and high yields.     

5H-[1,2,4]三嗪并[5,6-b]吲哚-3-硫醇类化合物的简便合成

报道了以2-甲(乙)基苯胺1a,1b为原料经Sandmeyer反应得到7-甲(乙)基靛红2a,2b;再以环境友好的聚乙二醇-400为溶剂,N-溴代丁二酰亚胺(NBS)为绿色溴代试剂对2a,2b进行5位溴代,得到5-溴-7-甲(乙)基靛红3a,3b;2a,2b,3a,3b进一步氮烃基化得到1-烃基-7-甲(乙)基靛红4a~4j和1-烃基-5-溴-7-甲(乙)基靛红5a~5j.2a,2b,3a,3b,4a~4j,5a~5j分别与硫代氨基脲,在以二氧六环为溶剂,碳酸钾存在的条件下回流反应,简便地合成了24种5H-[1,2,4]三嗪并[5,6-b]吲哚-3-硫醇类杂环化合物6a~6x.大部分化合物未见文献报道,其结构经红外光谱、质谱、核磁氢谱(碳谱)和元素分析确认.     

Hydrothermal synthesis of a mixed-valence hexamolybdate cluster: crystal structure of [HN(CH2CH2)3N]2[HMoVMoVI5O19]·[N(CH2CH2)3N]

The hydrothermal reaction of MoO₃, V, Na₂WO₄· 2H₂O, [N(CH₂CH₂)₃N](1,4-diazabicyclo[2.2.2] octane), and H₂O at 160°C for 90h gave dark-brown crystals of [HN(CH₂CH₂)₃N]₂[HMo^VMo^VI ₅O¹⁹]·[N(CH₂CH₂)₃N], (1), in 40% yield. Complex (1) is the first one-electron reduced mixed-valence hexamolybdate to be crystallized and structurally characterized. The crystal structure of (1) consists of discrete [HMo^VMo^VI ₅O₁₉]^2– anions, [HN-(CH₂CH₂)₃N]⁺ cations, and neutral [N(CH₂CH₂)₃N] molecules of crystallization.     

6-碘-5H-[1,2,4]三嗪并[5,6-b]吲哚-3-硫醇类化合物的合成

利用各种碘代的靛红为底物,与氨基硫脲在水-二氧六环(体积比为5:1)混合溶剂为反应介质,K2 CO3为碱条件下,进行缩合反应,有效合成了一系列结构新型的碘官能团化的[1,2,4]三嗪并[5,6-b]吲哚-3-硫醇类化合物.所合成的目标化合物结构均通过波谱数据和元素分析得以确认.