Synthesis and crystal structure of a new one-dimensional system with end-to-end single dicyanamide bridges between nickel(II) centres

The complex [Ni(tn)₂{N(CN)₂}]ClO₄ (tn=trimethylenediamine) has been synthesized and the structure has been determined. The complex forms a one-dimensional chain structure via the bidentate bridging ligand dicyanamide. A two-dimensional networks is formed via interchain hydrogen bond interactions.     

(TiNi)_x(x=2~4)团簇结构和电子结构

从团簇角度对TiNi形状记忆合金进行了量子化学从头算研究。设计并优化了等原子比(TiNi)x(x=2~4)簇的多种可能几何结构,并对较稳定构型进行电子结构的分析。结果表明,等原子比的(TiNi)n团簇以TiNi成键为主要分子骨架,小团簇有较多能量接近的异构体,TiTi成键对能量降低有较大贡献。     

Do intramolecular halogen bonds exist? Ab initio calculations and crystal structures’ evidences

Cl···O intramolecular contacts are analysed here. Hence the Cambridge Structural Database (CSD) search was performed to find five-membered Cl–C=C–C=O pseudo-rings closed through Cl···O intramolecular contacts. Such rings were analysed and it was found that some of Cl···O distances are smaller than the corresponding sum of van der Waals radii. Additionally ab initio MP2/6-311++G(d,p) calculations and AIM analyses were carried out here on 3-chloropropenal and its fluoro derivatives to deepen the nature of intramolecular Cl···O interactions, some of findings may indicate that they are attractive and stabilizing ones. This paper is dedicated to Prof. T. M. Krygowski on the occasion of his 70th birthday     

Borderline of hydrogen bonding of silanols

Two new silanols bearing very bulky silyl groups, (i-Pr₃ Si)₃SiOH and (t − BuMe₂Si)₃SiOH were prepared by peracidoxidation of their respective silanes. The X − ray crystallographic analysis revealed that (t − BuMe₂Si)₃ SiOH forms a dimeric structure with hydrogen bonding, while (i − Pr₃ Si)₃ SiOH exists as a monomer in the crystal. The effects of the size of the substituents as well as the reactivity of these silanols are discussed.     

Synthesis and Structure Characterization of a Tetranuclear Manganese(Ⅲ) Complex:[Mn4O2(O2CMe)6(MeOH)2(dbm)2]·2MeCOOH·2CH2Cl2

The title compound, [Mn4O2(O2CMe)6(MeOH)2(dbm)2]·2MeCOOH·2CH2Cl2 (Hdbm = dibenzoylmethane), has been synthesized and structurally determined by single-crystal X-ray diffraction. The crystal belongs to triclinic, space group P(-l), with a = 10.729(3), b = 12.269(3), c =13.085(4) (A), a = 106.367(3), β = 107.643(2), γ = 94.771(2)°, V = 1547.9(7) (A)3, Z = 1,C50H64Cl4Mn4O24, Mr= 1410.57, Dc= 1.513 g/em3, F(000) = 724, Rint = 0.0147, T = 293(2) K and μ = 1.046 mm-1. The fimal R = 0.0359 and wR = 0.0938 for 5791 observed reflections with I ＞ 2( )I).The structure of the complex consists of one [Mn4(μ3-O)2]8+ core with four coplanar Mn atoms disposed in an extended "butterfly-like" arrangement and two O atoms triply bridging each "wing",and the peripheral ligation is provided by six μ2-MeCO2-, two terminalμ2-dbm- groups at the two hydrogen bonding interactions are found within the structure of the compound.     

HCN及其氢加成物分子间氢键问题的量子化学研究

采用量子化学(MNDO、CNDO/2)方法,探讨了HCN、H_2CNH和H_3CNH_2分子间的N…H-C氢键的构成。计算表明:HCN-HCN分子间氢键作用较强,支持了实验结果。HCN及其氢加成物H_2CNH、H_3CNH_2等分子间的氢键作用依次减弱,其随C≡N、C=N、C-N的差异而变化,碳氮链中氮原子的作用是构成N…H-C型氢键的一个决定性因素。     

Excess enthalpies for mixtures of cyclohexanone with isomeric propanols and butanols at 298.15 K

Excess enthalpies (H ^E ) for mixtures of cyclohexanone with propan-1-ol. propan-2-ol, butan-1-ol, butan-2-ol and 2-methyl propan-1-ol at 298.15 K have been measured over the entire composition range. All mixed endothermically with the maximum values ofH ^E occurring at equimole fraction. Comments about the molecular interactions contributing to the excess enthalpies of a cyclic ketone + an alcohol are made on the basis of these results.     

Synthesis and Structural Characterization of a New Cadmium(Ⅱ) Complex Bridged by Endo-norbornene-cis-5,6-dicarboxylic Acid

A polynuclear complex [Cd(endc)(H2O)]n·nH2O (endc = endo-norbomene-cis5,6-dicarboxylate anion) has been synthesized by the hydrothermal reaction of cadmium nitrate tetrahydrate with endo-norbomene-cis-5,6-dicarboxylic acid in 1:1 molar ratio,and structurally characterized by single-crystal X-ray diffraction.It crystallizes in monoclinic,space group P21/c with a = 1.16471(7),b = 0.95334(7),c = 0.91109(9) nm,Z = 4,V= 1.01035(14)nm3,Dc.= 2.160 g/cm3,μ= 2.172 mm-1,F(000) = 648,R =0.0302 and wR = 0.0752.According to structural analysis,each Cd(Ⅱ) ion is coordinated to six O atoms from three endc anions and one water molecule,giving a distorted octahedral geometry.Two- dimensional layer arrangement of the title complex is constructed from the bridging nature of endc.It is worth notice that adjacent two-dimensional layers are joined together to form a three-dimensional supramolecular framework via intermolecular hydrogen bonding interactions.     

A Novel Hybrid Solid Constructed from Tetramolybdate and Copper Complexes with Mixed Ligands: [{(Cu·phen)2(tp)}{(Cu·phen·H2O)2(tp)}{Mo4O14}]

A novel copper molybdate with mixed ligands, [{(Cu·phen)2(tp)}{(Cu·phen·H2O)2(tp)}{Mo4O14}] (phen=1,10-phenanthroline, tp=terephthalate) 1, has been hydrothermally synthesized and structurally characterized. The crystal belongs to monoclinic system, space group P21/c with a=13.1711(7), b=19.6132(10), c=13.6910(7) (A), β=117.6870(10)°, V=3131.8(3)(A)3, Z=2, C64H44Cu4Mo4N8O24, Mr=1946.99, Dc=2.065 g/cm3, F(000)=1920, μ(MoKα) (A) 2.198 mm-1, R=0.0810 and wR=0.2012 for 4233 observed reflections (Ⅰ ＞ 2σ(Ⅰ)). The structural analysis indicates that the title compound contains a discrete tetramolybdate cluster decorated with copper complex fragments and tp ligands bridging the clusters into a wave-like layer. The hydrogen bonding between adjacent layers further extends the compound into a 3-D framework.     

电沉积羟基磷灰石/TiO2复合涂层

结合强度;电沉积羟基磷灰石/TiO2复合涂层