A trinuclear palladium(II) complex containing N,S‐coordinating 2‐(benzylsulfanyl)anilinide and 1,3‐benzothiazole‐2‐thiolate ligands with a central square‐planar PdN4 motif

The reaction of dichlorido(cod)palladium(II) (cod = 1,5‐cyclooctadiene) with 2‐(benzylsulfanyl)aniline followed by heating in N,N‐dimethylformamide (DMF) produces the linear trinuclear Pd₃ complex bis(μ₂‐1,3‐benzothiazole‐2‐thiolato)bis[μ₂‐2‐(benzylsulfanyl)anilinido]dichloridotripalladium(II) N,N‐dimethylformamide disolvate, [Pd₃(C₇H₄NS₂)₂(C₁₃H₁₂NS)₂Cl₂]·2C₃H₇NO. The molecule has symmetry and a Pd...Pd separation of 3.2012 (4) Å. The outer Pd^II atoms have a square‐planar geometry formed by an N,S‐chelating 2‐(benzylsulfanyl)anilinide ligand, a chloride ligand and the thiolate S atom of a bridging 1,3‐benzothiazole‐2‐thiolate ligand, while the central Pd^II core shows an all N‐coordinated square‐planar geometry. The geometry is perfectly planar within the PdN₄ core and the N—Pd—N bond angles differ significantly [84.72 (15)° for the N atoms of ligands coordinated to the same outer Pd atom and 95.28 (15)° for the N atoms of ligands coordinated to different outer Pd atoms]. This trinuclear Pd₃ complex is the first example of one in which 1,3‐benzothiazole‐2‐thiolate ligands are only N‐coordinated to one Pd centre. The 1,3‐benzothiazole‐2‐thiolate ligands were formed in situ from 2‐(benzylsulfanyl)aniline.     

Synthesis and Crystal Structure of a Decanuclear Silver（I）-thiolate Compound Ag10S[S2P（OEt）2]8

A new decanuclear silver(I) compound Ag₁₀(μ₈‐S)(dtp)₈ [dtp=S₂P(OEt)₂] was isolated from a reaction mixture containing W₂S₄(dtp)₂ and AgN0₃, and its solid‐state molecular structure was determinated by X‐ray crystallography. The crystallographic study revealed that the compound contains a distorted mono‐capped quasi‐prism [Ag_io] with an octat‐bridging S atom at the center of the prism. The compound (C₃₂H₈₀Ag₁₀O₁₆P₈S₁₇, M_r=2592.46) crystallizes in the monoclinic P2₁/n space group, with a = 1.5111(5) nm, b=2.3656(8) nm, c=2.284(1) nm, β= 96.88(3)°, V=8.107(5) nm³, Z=4 and D,=2.12 g · cm^?3. The solution using direct method and full‐matrix least‐squares refinement led to R=0.066, Rw=0.078 for 3928 reflections with I3σ(I).     

A novel three‐dimensional AgI coordination polymer based on mixed naphthalene‐1,5‐disulfonate and aminoacetate ligands

The three‐dimensional coordination polymer poly[[bis(μ₃‐2‐aminoacetato)di‐μ‐aqua‐μ₃‐(naphthalene‐1,5‐disulfonato)‐hexasilver(I)] dihydrate], {[Ag₆(C₁₀H₆O₆S₂)(C₂H₄NO₂)₄(H₂O)₂]·2H₂O}_n, based on mixed naphthalene‐1,5‐disulfonate (L1) and 2‐aminoacetate (L2) ligands, contains two Ag^I centres (Ag1 and Ag4) in general positions, and another two (Ag2 and Ag3) on inversion centres. Ag1 is five‐coordinated by three O atoms from one L1 anion, one L2 anion and one water molecule, one N atom from one L2 anion and one Ag^I cation in a distorted trigonal–bipyramidal coordination geometry. Ag2 is surrounded by four O atoms from two L2 anions and two water molecules, and two Ag^I cations in a slightly octahedral coordination geometry. Ag3 is four‐coordinated by two O atoms from two L2 anions and two Ag^I cations in a slightly distorted square geometry, while Ag4 is also four‐coordinated by two O atoms from one L1 and one L2 ligand, one N atom from another L2 anion, and one Ag^I cation, exhibiting a distorted tetrahedral coordination geometry. In the crystal structure, there are two one‐dimensional chains nearly perpendicular to one another (interchain angle = 87.0°). The chains are connected by water molecules to give a two‐dimensional layer, and the layers are further bridged by L1 anions to generate a novel three‐dimensional framework. Moreover, hydrogen‐bonding interactions consolidate the network.     

A three‐dimensional metal–organic polymer: poly[bis(μ2‐pyrimidine‐2‐thiolato‐κ4N1,S:S,N3)lead(II)]

The title compound, [Pb(C₄H₃N₂S)₂]_n, was prepared by the reaction of [Pb(OAc)₂]·3H₂O (OAc is acetate) with pyrimidine‐2‐thione in the presence of triethylamine in methanol. In the crystal structure, the Pb^II atom has an N₄S₄ coordination environment with four ligands coordinated by N‐ and S‐donor atoms. This compound shows that the pyrimidine‐2‐thiolate anion can lead to a three‐dimensional network when the coordination number of the metal ion can be higher than 6, as is the case with the Pb^II ion. This compound presents only covalent bonds, showing that despite the possibility of the hemidirected geometries of Pb^II, the eight‐coordinated ion does not allow the formation of an isolated molecular structure with pyrimidine‐2‐thiolate as the ligand.     

A novel crystal structure of {tris[4‐(1H‐pyrazol‐3‐yl‐κN2)‐3‐azabut‐3‐enyl]amine‐κN}iron(II) bis(tetrafluoridoborate) methanol monosolvate featuring a low‐spin configuration

Mononuclear complexes are good model systems for evaluating the effects of different ligand systems on the magnetic properties of iron(II) centres. A novel crystal structure of the title compound, [Fe(C₁₈H₂₄N₁₀)](BF₄)₂·CH₃OH, with one molecule of methanol per formula unit exhibits a strictly sixfold coordination sphere associated with a low‐spin configuration at the metal centre. The incorporated methanol solvent molecule promotes extended hydrogen‐bonding networks between the tetrafluoridoborate anions and the cationic units. A less constrained crystal structure regarding close contacts between the tetrafluoridoborate anions and the cationic units allows a spin transition which is inhibited in the previously published hydrate of the title compound.     

配位聚合物[Cu(pa)(vim)2]n的合成、晶体结构和电化学性质研究

本文合成了一种新型配位聚合物[Cu(pa)(vim)2]n(pa为邻苯二甲酸阴离子,vim为1-乙烯基-1H-咪唑),并用x射线单晶衍射仪和元素分析表征了其单晶结构。晶体属单斜晶系,C2/c空间群,晶胞参数分别为：a＝1.6527(3) nm, b＝0.81800(16) nm, c＝1.4463(3) nm, β＝113.19(3)°, V＝1.7973(7) nm3, Z＝4, Dc＝1.537 g?cm－3。 [I＞2σ(I)]时：R1＝0.0476, wR2＝0.1235,对所有数据：R1＝0.0693, wR2＝0.1355。配合物的结构中存在沿着c轴的zigzag聚合链。每个铜原子位于晶体中心,与两个N原子和两个O原子进行配位,形成了扭曲的平面结构。电化学研究表明在配合物中Cu2+/Cu+的氧化还原是一个单电子的准可逆过程。     

Synthesis,crystal structure and magnetic property of a novel ion‐pair nickel(III) complex containing 1,2‐benzenedithiolate

A new ion‐pair complex [1‐(4‐nitrobenzyl)pyridinium][Ni(bdt)₂] (1), in which bdt^2? = 1,2‐benzenedithiolate, has been synthesized and characterized. The X‐ray structure analysis shows that the anions are centrosymmetric, the two non‐equivalent anions form different uniform‐spaced stacking pattern and the weak H‐bonding interactions of C? H…S were observed in 1. The temperature dependence of magnetic susceptibilities of 1 indicates ferromagnetic behavior in the antiferromagnetic exchange system, which may arise from spin‐canting. Copyright © 2007 John Wiley & Sons, Ltd.     

Preparation, Crystal Structure and Properties of a Pentametallic 3-Ferrocenyl-2-crotonic acid-Bridged Copper（Ⅱ） Complex

The synthesis and characterization of the copper (II) complex [Cu₂(OOCCH = C(CH₃)Fc)₃(phen)₂]CIO₄ · 2H₂O (1) are reported. The structure of the complex was determined by single‐crystal X‐ray analysis. The compound crystallizes in the monoclinic system, space group Pc, with Z =2, a = 1.2799(4) nm, b =0.9969 (4) nm, c = 2.5228 nm, and β = 91.576 (1) °. The cationic part of 1 indicates a penametallic core in which three 3‐ferrocenyl‐2‐crotonic acid salt (FCA) groups act as (O, O') bridging ligands between two copper (II) ions with a square‐pyramidal environment. Cyclic voltammetric experiments in acetonitrile have been performed mainly to examine the Fe(II) → Fe(III) one‐electron oxidation in FCA and its complex. The variable‐temperature magnetic susceptibility measurements revealed very weak intramolecular anti‐ferromagnetic coupling. Fitting parameters are 2J = ‐0.2 cm^?1, g = 2.114, and θ = 0K.     

Crystallographic report: Crystal and molecular structure of triphenyltin thiazole‐2‐carboxylate

The tin atom in the title compound is in a distorted C₃O tetrahedral geometry, as the carboxylate ligand is effectively monodentate. Copyright © 2004 John Wiley & Sons, Ltd.     

Photoluminescence properties of a cationic trinuclear zinc(II) complex with the tetradentate Schiff base ligand 6‐methyl‐2‐({[(pyridin‐2‐yl)methyl]imino}methyl)phenolate

Metal complexes with Schiff base ligands have been suggested as potential phosphors in electroluminescent devices. In the title complex, tetrakis[6‐methyl‐2‐({[(pyridin‐2‐yl)methyl]imino}methyl)phenolato‐1:2κ⁸N,N′,O:O;3:2κ⁸N,N′,O:O]trizinc(II) hexafluoridophosphate methanol monosolvate, [Zn₃(C₁₄H₁₃N₂O)₄](PF₆)₂·CH₃OH, the Zn^II cations adopt both six‐ and four‐coordinate geometries involving the N and O atoms of tetradentate 6‐methyl‐2‐({[(pyridin‐2‐yl)methyl]imino}methyl)phenolate ligands. Two terminal Zn^II cations adopt distorted octahedral geometries and the central Zn^II cation adopts a distorted tetrahedral geometry. The O atoms of the phenolate ligands bridge three Zn^II cations, forming a dicationic trinuclear metal cluster. The title complex exhibits a strong emission at 469 nm with a quantum yield of 15.5%.     

Luminescent Property of a Supramolecular Silver(I)‐Thiolate Complex Based on Secondary Ag‐S Interactions and Hydrogen Bonds

The supramolecular silver(I)‐thiolate complex [Ag(μ₂‐SC₄N₂H₄)₂(SCN)]_n has been prepared from the reaction of AgSCN and pyrimidine‐2‐thiol in DMF. X‐ray diffraction analysis shows that the supramolecular structure exhibits one‐dimensional chain through the secondary Ag‐S interactions and the chains are further linked by strong hydrogen bonds to form a three dimensional network. The luminescence effect from the silver‐centered state of S→Ag LMCT in solid state is different from that in solution due to the secondary Ag‐S interactions.     

[ZnL2Cl2]·2H2O (L = N’-苯甲酰基异烟酰肼)的合成、晶体结构及其表征

标题化合物中，锌（Ⅱ）为四配位畸变的四面体构型。通过相邻分子之间的氢键把配合物连接成三维网络结构，而且，配合物中吡啶环与苯环之间存在着面-面的π–π相互作用。配体与配合物均可发出蓝色荧光，其固态时的最大发射峰为480 nm。     

Copper(II) bromide,nitrate and perchlorate complexes with sterically demanding N‐(6‐methylpyridin‐2‐yl)acetamide ligands

Functionalized acid amides are widely used in biology, medicine, environmental chemistry and many other areas. Among them, pyridine‐substituted amides, in particular N‐(pyridin‐2‐yl)acetamide and its derivatives, play an important role due to their excellent chelating properties. The donor properties of these ligands can be effectively modified by introducing electron‐donating substituents (e.g. alkyl groups) into the heterocycle. On the other hand, substituents in the α‐position of the pyridine ring can create steric hindrance, which significantly influences the coordination number and geometry. To achieve a better understanding of these effects, copper(II) complexes with sterically demanding N‐(6‐methylpyridin‐2‐yl)acetamide ligands (L ) and monoanions of different size, shape and coordination ability have been chosen as model compounds. The crystal structures of three new compounds, bromidobis[N‐(6‐methylpyridin‐2‐yl‐κN )acetamide‐κO ]copper(II) bromide, [CuBr(C₈H₁₀N₂O)]Br, (I), aquabis[N‐(6‐methylpyridin‐2‐yl‐κN )acetamide‐κO ]copper(II) dinitrate, [Cu(C₈H₁₀N₂O)(H₂O)](NO₃)₂, (II), and aquabis[N‐(6‐methylpyridin‐2‐yl‐κN )acetamide‐κO ]copper(II) bis(perchlorate), [Cu(C₈H₁₀N₂O)(H₂O)](ClO₄)₂, (III), have been determined by single‐crystal X‐ray diffraction analysis. It has been shown that the presence of the 6‐methyl group results in either a distorted square‐pyramidal or a distorted trigonal–bipyramidal coordination geometry around the Cu^II centres instead of the typical octahedral geometry observed when the methyl substituent is absent or occupies any other position on the pyridine ring. Moreover, due to the steric hindrance provided by the L ligands, only the bromide ligand, the smallest of the series, enters into the first coordination sphere of the Cu^II ion in (I). In (II) and (III), the vacant coordination site of the Cu^II ion is occupied by a water molecule, while the nitrate and perchlorate anions are not involved in coordination to the metal centre. The structures of (I)–(III) are characterized by the presence of one‐dimensional infinite chains formed by hydrogen bonds of the types N—H…Br [in (I)], N—H…O and O—H…O [in (II) and (III)] between the amide groups of the L ligands, the coordinated water molecules and the uncoordinated anions. The hydrogen‐bonded chains are further interconnected through π–π stacking interactions between the pyridine rings of the L ligands, with approximate interplanar separations of 3.5–3.6 Å.     

Construction and photoluminescence properties of a three‐dimensional ZnII coordination network based on naphthalene‐1,4‐dicarboxylic acid and 1,6‐bis(pyridin‐3‐yl)‐1,3,5‐hexatriene

In recent years, coordination polymers constructed from multidentate carboxylate and pyridyl ligands have attracted much attention because these ligands can adopt a rich variety of coordination modes and thus lead to the formation of crystalline products with intriguing structures and interesting properties. A new coordination polymer, namely poly[[μ₂‐1,6‐bis(pyridin‐3‐yl)‐1,3,5‐hexatriene‐κ²N:N′](μ₃‐naphthalene‐1,4‐dicarboxylato‐κ⁴O¹,O^1′:O⁴:O^4′)zinc(II)], [Zn(C₁₂H₆O₄)(C₁₆H₁₄N₂)]_n, has been prepared by the self‐assembly of Zn(NO₃)₂·6H₂O, naphthalene‐1,4‐dicarboxylic acid (1,4‐H₂ndc) and 1,6‐bis(pyridin‐3‐yl)‐1,3,5‐hexatriene (3,3′‐bphte) under hydrothermal conditions. The title compound has been structurally characterized by IR spectroscopy, elemental analysis, powder X‐ray diffraction and single‐crystal X‐ray diffraction analysis. Each Zn^II ion is six‐coordinated by four O atoms from three 1,4‐ndc²⁻ ligands and by two N atoms from two 3,3′‐bphte ligands, forming a distorted octahedral ZnO₄N₂ coordination geometry. Pairs of Zn^II ions are linked by 1,4‐ndc²⁻ ligands, leading to the formation of a two‐dimensional square lattice ( sql ) layer extending in the ab plane. In the crystal, adjacent layers are further connected by 3,3′‐bphte bridges, generating a three‐dimensional architecture. From a topological viewpoint, if each dinuclear zinc unit is considered as a 6‐connected node and the 1,4‐ndc²⁻ and 3,3′‐bphte ligands are regarded as linkers, the structure can be simplified as a unique three‐dimensional 6‐connected framework with the point symbol 4⁴6¹⁰8. The thermal stability and solid‐state photoluminescence properties have also been investigated.     

Disentangling steric and electronic factors in monomeric bis(2‐bromo‐4‐chloro‐6‐{[(2‐hydroxyethyl)imino]methyl}phenolato‐κ2N,O)copper(II)

The title compound, [Cu(C₉H₈BrClNO₂)₂], is a square‐planar complex. The potentially tridentate dibasic 2‐bromo‐4‐chloro‐6‐{[(2‐hydroxyethyl)imino]methyl}phenolate ligand coordinates in a trans‐bis fashion to the Cu^II centre via the imine N and phenolate O atoms. The Cu^II atom lies on the centre of inversion of the molecule. The potentially coordinating hydroxyethyl group remains protonated and uncoordinated, taking part in intermolecular hydrogen bonds with vicinal groups, leading to the formation of a two‐dimensional hydrogen‐bond network with sheets parallel to the (10) plane. Substituent effects on the crystal packing and coordination modes of the ligand are discussed.     

An Efficient One-pot Synthesis of β-Amino/β-Acetamido Carbonyl Compounds via ZrCl4-catalyzed Mannich-type Reaction

Zirconium(IV) chloride catalyzed efficient one-pot synthesis of β-amino/β-acetamido carbonyl compounds at room temperature is described. In the presence of ZrCl4, the three-component Mannich-type reaction via a variety of in situ generated aldimines, with various ketones, aromatic aldehydes and aromatic amines in ethanol, led to the formation of β-amino carbonyl compounds and the four-component Mannich-type reaction of aromatic aldehydes with various ketones, acetonitrile and acetyl chloride resulted in the corresponding β-acetamido carbonyl compounds in high to excellent yields. This methodology has also been applied towards the synthesis of dimeric β-amino/β-acetamido carbonyl compounds.     

A new one‐dimensional CdII coordination polymer with a two‐dimensional layered structure incorporating 2‐[(1H‐imidazol‐1‐yl)methyl]‐1H‐benzimidazole and benzene‐1,2‐dicarboxylate ligands

The N‐heterocyclic ligand 2‐[(1H‐imidazol‐1‐yl)methyl]‐1H‐benzimidazole (imb) has a rich variety of coordination modes and can lead to polymers with intriguing structures and interesting properties. In the coordination polymer catena‐poly[[cadmium(II)‐bis[μ‐benzene‐1,2‐dicarboxylato‐κ⁴O¹,O^1′:O²,O^2′]‐cadmium(II)‐bis{μ‐2‐[(1H‐imidazol‐1‐yl)methyl]‐1H‐benzimidazole}‐κ²N²:N³;κ²N³:N²] dimethylformamide disolvate], {[Cd(C₈H₄O₄)(C₁₁H₁₀N₄)]·C₃H₇NO}_n, (I), each Cd^II ion exhibits an irregular octahedral CdO₄N₂ coordination geometry and is coordinated by four O atoms from two symmetry‐related benzene‐1,2‐dicarboxylate (1,2‐bdic²⁻) ligands and two N atoms from two symmetry‐related imb ligands. Two Cd^II ions are connected by two benzene‐1,2‐dicarboxylate ligands to generate a binuclear [Cd₂(1,2‐bdic)₂] unit. The binuclear units are further connected into a one‐dimensional chain by pairs of bridging imb ligands. These one‐dimensional chains are further connected through N—H…O hydrogen bonds and π–π interactions, leading to a two‐dimensional layered structure. The dimethylformamide solvent molecules are organized in dimeric pairs via weak interactions. In addition, the title polymer exhibits good fluorescence properties in the solid state at room temperature.     

First principles study on the structure and electronic properties of 2‐nitrimino‐1‐nitroimidazolidine

The properties of 2‐Nitrimino‐1‐nitroimidazolidine are calculated by using SIESTA code, which adopts the standard Kohn‐Sham self‐consistent density functional method in the local density approximation. The structures and electronic properties are analyzed, and the factors that affect the impact sensitivity are discussed based on the crystal structure, band energy, and projected density of state. The reason for the smaller impact sensitivity compared to RDX (hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine) is also explored from several respects such as the weakest bond dissociation energy in single molecule, and hydrogen bond, band gap in the crystal. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Combining valproate and bipyridyl ligands to construct a 0D core‐shell Zn5(μ3‐OH)2 cluster and a 2D layered coordination network with a [Zn3(μ3‐OH)]2 SBU

Starting from the proposed zinc carboxylate cluster tetrakis(μ‐2‐propylpentanoato)dizinc(II), Zn₂(μ₂‐valp)₄ ( I ), of valproic acid, a branched short‐chain fatty acid, and bipyridine ligands, two new mixed‐ligand coordination compounds, namely, bis(2,2′‐bipyridine)di‐μ₃‐hydroxido‐hexakis(μ‐2‐propylpentanoato)bis(2‐propylpentanoato)pentazinc(II), [Zn₅(C₈H₁₅O₂)₈(OH)₂(C₁₀H₈N₂)₂] ( II ), and poly[[bis(μ‐4,4′‐bipyridine)di‐μ₃‐hydroxido‐octakis(μ‐2‐propylpentanoato)bis(2‐propylpentanoato)hexazinc(II)] dimethylformamide disolvate], {[Zn₆(C₈H₁₅O₂)₁₀(OH)₂(C₁₀H₈N₂)₂]·2C₃H₇NO}_n ( III ), were synthesized. Compound II is a core‐shell‐type zero‐dimensional discrete Zn₅(μ₃‐OH)₂ metal–organic cluster with Zn ions in double‐triangle arrangements that share one Zn ion coincident with an inversion centre. The cluster contains three crystallographically non‐equivalent Zn ions exhibiting three different coordination geometries (tetrahedral, square pyramidal and octahedral). The cluster cores are well separated and embedded in a protective shell of the aliphatic branched short chains of valproate. As a result, there is no specific interaction between the discrete clusters. Conversely, compound III , a 2D layered coordination network with a secondary building unit (SBU), is formed by Zn₆(μ₃‐OH)₂ clusters exhibiting a chair‐like hexagonal arrangement. This SBU is formed from two Zn₃(μ₃‐OH) trimers related by inversion symmetry and connected by two syn–anti bridging carboxylate groups. Each SBU is connected by four 4,4′‐bipyridine ligands producing a 6³‐hcb net topology. 2D coordination layers are sandwiched within layers of dimethylformamide molecules that do not interact strongly with the network due to the hydrophobic protection provided by the valproate ligands.     

N-(4-甲基苯甲酰氨基) N’-[5-(2-三氟甲基苯基)-2-呋喃甲酰硫脲的合成、晶体结构测定与生物活性测定

本文首次合成标题化合物N-(4-甲基苯甲酰氨基)-N’-[5-(2-三氟甲基苯基)-2-呋喃甲酰硫脲。化合物(C21H16F3N3O3S, Mr = 447.43)单晶经测定为单斜晶体,空间群为P -1。在晶体中,存在一些分子内和分子间的相互作用,分子间还有C—H···π 的相互作用,这可能导致晶体更稳定的原因。目标产物的结构经IR, H NMR和元素分析测定确证。初步生物活性测试表明,部分化合物对棉花枯萎病、黄瓜灰霉病、苹果轮纹病和棉花炭疽病有较好的选择性杀菌活性;部分目标化合物有较好的除草活性。