一维链配位聚合物[Mn(acacen){N(CN)2}]n的合成、结构和性质的研究(英)

The manganese(Ⅲ) complex [Mn(acacen){N(CN)₂}]_n [H₂acacen=bis(acetylacetone)ethylenediimine] has been synthesized and the structure has been determined. The complex forms a one-dimensional chain structure via the bidentate bridge ligand μ_1,5-[N(CN)₂]^- linking [Mn(acacen)] moiety. The magnetic property of the compound (75～300 K) shows the existence of an antiferromagnetic exchange interaction among paramagnetic centers along the chain. CCDC: 244940.     

锰/钴-二氰胺-4-(1-咪唑基)苯胺三元配合物的合成与结构表征

以二氰胺钠[Na(dca)]和4-(1-咪唑基)苯胺(L)为共配体分别与锰盐和钴盐反应合成了2种新的配合物：零维[Mn(L)₂(dca)₂(H₂O)₂] (1)和二维[Co(L)₂(dca)](dca)_0.5(ClO₄)_0.5·1.5H₂O·MeOH (2)。通过元素分析、红外光谱和X射线单晶衍射对其进行了表征。配合物1属于三斜晶系，P1空间群。配合物2晶体属于正交晶系，Cmcm空间群。配合物1是1个中心对称的单核结构，锰(Ⅱ)离子与分别来自2个dca和2个L配体的4个氮原子以及2个水分子配位，形成八面体配位几何，L和dca均为单齿配位；配合物2是由混合桥dca和L组装成的二维配位聚合物网状结构，相邻的二维网以面对面方式堆积，沿c轴方向形成一维孔道，里面填充着未配位的反离子和溶剂分子。     

两个含有平行交替链的新型二氰胺配位高聚物: {Mn(dmpz)[N(CN)2]2}2和{Cu(dmpz)[N(CN)2]2}2

Two new dicyanamide coordination polymers, {Mn(dmpz)[N(CN)2]2}2 (1) and {Cu(dmpz)[N(CN)2]2}2 (2)(dmpz=3,5-dimethylpyrazole), were synthesized and characterized by single crystal X-ray diffraction analysis and IR spectroscopy. In 1 and 2 the metal ions have two different coordination modes, where one is coordinated to four dicyanamide anions and two monodentate dmpz molecules to form a slightly distorted octahedral geometry, while the other adopts octahedral geometry, surrounded by four nitrile N atoms and two amide N atoms of the dicyanamide anions. Both complexes contain two alternating chains that are parallel to each other.     

A New One-dimensional Dicyanamide Bridged Zinc(II) Complex Containing Nitronyl Nitroxide Radicals:Synthesis,Crystal Structure and Magnetic Properties

A new one-dimensional dicyanamide bridged zinc(II) complex containing nitronyl nitroxide radicals Zn(NO3)(NIT-1'-MeBzIm)(dca)n·(H2O)n(NIT-1'-MeBzIm = 2-{2'-(l'-me-thyl)benzimidazolyl}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, dca = dicyanamide anion) has been prepared and structurally characterized by single-crystal X-ray diffraction.The complex crystallizes in triclinic, space group P1, with a = 7.428(3), b = 9.839(3), c = 16.708(6), α = 93.270(4), β = 101.642(4), γ = 100.632(4)°, C17.5H21N8O5.5Zn, Mr = 496.79, V = 1169.7(7) 3, Dc = 1.411 g/cm3, μ(MoKα) = 1.096 mm-1, Z = 2, F(000) = 512, R = 0.0583 and wR = 0.1663 for 4295 observed reflections with I > 2σ(I).X-ray analysis reveals that the zinc(II) ion is six-coordinated with a distorted octahedral geometry.These units develop as 1D species where dicyanamide ligands bridge zinc(II) ions.In addition, molecules are linked by π-π piling interactions to form 1-D double-chains.Magnetic investigation indicates that the weak intramolecular interactions are antiferromagnetic with J =-0.27 cm?1, where the spin Hamitonian is defined as H =-2∑i,jJi,jSiS within the complex.     

A three‐dimensional anionic metal–dicyanamide network in poly[ethyltriphenylphosphonium [tri‐μ2‐dicyanamidato‐cadmium(II)]]

The title compound, (C₂₀H₂₀P)[Cd(C₂N₃)₃], consists of ethyltriphenylphosphonium (EtPh₃P⁺) cations filling voids in a three‐dimensional anionic cadmium dicyanamide network. In the structure, each Cd^II atom is connected to six neighbouring Cd^II atoms through six separate dicyanamide ligands, forming cube‐shaped cages. The three‐dimensional anionic network encloses a solvent‐accessible void space of 1851 ų, amounting to 69.3% of the unit‐cell volume. Each cage accommodates only one EtPh₃P⁺ cation.     

A new two‐dimensional polymeric cadmium(II) complex containing dicyanamide bridging ligands

As part of an exploration of new coordination polymers, a cadmium‐dicyanamide complex, namely poly[benzyltriethylammonium [tri‐μ‐dicyanamido‐κ⁶N ¹:N⁵‐cadmium(II)]], {(C₁₃H₂₂N)[Cd(C₂N₃)₃]}_n , has been synthesized by the reaction of benzyltriethylammonium bromide, cadmium nitrate tetrahydrate and sodium dicyanamide in aqueous solution, and characterized by single‐crystal X‐ray diffraction at room temperature. In the crystal structure, each Cd^II cation is coordinated by six nitrile N atoms from six anionic dicyanamide (dca) ligands to furnish a slightly distorted octahedral geometry. Neighbouring Cd^II cations are linked by dicyanamide bridges to construct a two‐dimensional anionic layer coordination polymer. One amide N atom in the bridging dca ligand is disordered over two sites. The cations lie between the anionic frameworks and there are no hydrogen‐bond interactions between the cations and anions. The organic cations are not involved in the formation of the supramolecular network.     

Synthesis,Crystal Structure and Ferromagnetic Properties of a New Dicyanamide Bridged Dicopper（Ⅱ） Complex with IM-1＇-MeBzIm-k2 N,O Mode

A new dinuclear copper（Ⅱ） complex with imino nitroxide radicals [Cu2（NO3）2（IM- 1 ′-MeBzIm）2（dca）2] （IM-1 ′-MeBzIm = 2-{2′-[（1′-methyl）benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl, dca = dicyanamide anion） has been prepared and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in triclinic, space group P 1^-, with α = 9.440（5）, b = 10.124（6）, c = 11.603（7） A, α = 102.904（7）, β = 94.033（6）,γ = 104.299（7）°, C34H40Cu2N16O8, Mr = 927.90, V= 1038.2（10） A^3, Z = 1, Dc = 1.484 g/cm^3, μ（MoKα） = 1.093 mm^-1, F（000） = 478, R = 0.0609 and wR = 0.1512 for 2889 observed reflections with Ⅰ 〉 2σ（I）. X-ray analysis reveals that two Cu（Ⅱ） atoms are bridged by two dicyanamides to form a centrosymmetric Cu（Ⅱ）-Cu（Ⅱ） dinuclear entity. Every Cu（Ⅱ） ion is five-coordinated with a distorted square pyramidal coordination geometry and IM-1′-MeBzlm ligand coordinates to the metal ion with the k^2 N（1 ′-MeBzlm）, O（IM） mode to avoid steric hindrance with the methyl group in the complex. Meanwhile, the molecules are linked by intermolecular hydrogen bonds, leading to a 1-D chain structure. Moreover, such chains are further linked by π-π stacking interactions to form a 2-D network structure. Magnetic measurement demonstrates that the intramolecular exchange couplings between Cu（Ⅱ） ion and the IM-1 ′-MeBzIm are ferromagnetic with J = 12.46 cm^-1, where the spin Hamitonian is defined as H^ = -2JS^1S^2 within the complex.     

Synthesis and Crystal Structure of a Cadmium Coordination Polymer with Dicyanamide and 1,2-Bis（1,2,4-triazol- 1-yl）ethane

The new cadmium(II) coordination polymer [Cd(bte)2(dca)2]n 1 (bte = 1,2-bis(1,2,4- triazol-1-yl)ethane, dca = dicyanamide) was synthesized and characterized by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 8.7148(15), b = 8.6142(17), c = 15.204(3) A, β = 92.100(10)o, V = 1140.6(4) A3, Z = 2, Mr = 572.87, Dc = 1.668 g/cm3, F(000) = 572, μ = 1.004 mm-1, the final R = 0.0654 and wR = 0.1429 for 1737 observed reflections (I > 2σ(I)). The cadmium atom is coordinated equatorially by four nitrogen atoms from four bte ligands and axially by two nitrogen atoms from two dca anions to adopt a distorted octahedral geometry. Each bte molecule bridges two cadmium(II) atoms. Two strands of bte molecules are wrapped around each other, and held together by cadmium(II) atoms. 1 Forms a double chain structure containing eighteen-membered Cd2(bte)2 rings.     

Spectral,structural and theoretical study of the effects of thiocyanato and dicyanamido ligands on the geometry of PbII complexes containing a triazinic ligand

Two lead(II) complexes of 5,6‐bis(furan‐2‐yl)‐3‐(pyridin‐2‐yl)‐1,2,4‐triazine (DFPT), namely one‐dimensional (1D) catena‐poly[[bis[5,6‐bis(furan‐2‐yl)‐3‐(pyridin‐2‐yl‐κN)‐1,2,4‐triazine‐κN²]lead(II)]‐di‐μ‐thiocyanato‐κ²N:S;κ²S:N], [Pb(NCS)₂(C₁₆H₁₀N₄O₂)₂]_n, 1 , and binuclear di‐μ‐dicyanamido‐κ²N¹:N⁵;κ²N⁵:N¹‐bis{[5,6‐bis(furan‐2‐yl)‐3‐(pyridin‐2‐yl‐κN)‐1,2,4‐triazine‐κN²](nitrato‐κ²O,O′)lead(II)}, [Pb₂(C₂N₃)₂(NO₃)₂(C₁₆H₁₀N₄O₂)₄], 2 , as well as DFPT itself, were prepared and identified by elemental analysis, FT–IR, ¹H NMR spectroscopy and single‐crystal X‐ray structural analyses. In the double‐chain 1D coordination polymer of 1 and the binuclear structure of 2 , the Pb atom has a hemidirected‐PbN₆S₂ and a rare holodirected‐PbN₆O₂ environment, respectively, with a distorted cubic geometry. All the coordination modes of dicyanamide ligands within lead complexes were studied using the Cambridge Structural Database (CSD) to compare them with the structures of 1 and 2 . In addition to hydrogen bonds, the crystal networks are stabilized by π–π stacking interactions between the triazine, furyl and pyridine aromatic rings. The most stable theoretical structures of the title compounds predicted by density functional theory (DFT) calculations were compared with the solid‐state results.     

二氰胺1-羟乙基-3-甲基咪唑离子液体的合成及对糖类化合物的溶解性能

根据离子液体结构-性能的关系,设计合成了一种新的低熔点、低黏度的功能化离子液体二氰胺1-羟乙基-3-甲基咪唑[Hemim][N(CN)2],并在298.2～353.2K的温度范围内测定了α-D-木糖、α-D-葡萄糖、D-果糖、蔗糖、D-乳糖、麦芽糖、棉子糖和木聚糖在该离子液体中的溶解度,计算了糖类化合物在离子液体中的标准溶解热力学参数.实验结果表明,除木聚糖外其他糖类化合物在[Hemim][N(CN)2]中均具有较高的溶解度,且其溶解度随着温度的升高显著增大.木聚糖属于多聚糖,溶解度较小,但温度效应非常明显.糖类化合物的溶解热力学参数SΔGo、TΔSSo和ΔHSo均为正值,且ΔHSoTΔSSo,说明溶解为焓控制过程.红外光谱结果表明,在溶解过程中木聚糖的氢键受到了一定程度的破坏,但它的结构并未发生明显的变化.