Crystal structure and luminescence property of novel three-dimensional network of {Eu2(p-BDC)3(Phen)2(H2O)2}n

The single crystal of a supramolecule, {Eu₂(p-BDC)₃(Phen)₂(H₂O)₂}_n (p-BDC=1,4-benzenedicarboxylate), with characteristic luminescence of Eu³⁺ was obtained by means of soft chemistry. The crystal structure determination reveals that each Eu³⁺ ion is coordinated by five oxygen atoms of p-BDC anions, one oxygen atom from water molecule, and two nitrogen atoms of Phen, respectively, resulting in an eight-coordinated Eu³⁺ center and a distorted square antiprism coordination polyhedron. Four bridges, two carboxylates of μ₄-p-BDC and two of μ₃-p-BDC, connect two Eu atoms into a binuclear unit. Moreover, the μ₃-p-BDC integrates the binuclear building blocks at the direction of b axis and the μ₄-p-BDC polymerizes the structure roughly along the direction of the sum vector of axis b and c, respectively, forming two-dimensional layers. Hydrogen bonds between layers make the structure a three-dimensional network. The luminescence spectra measured under 77 K demonstrate the antenna effect of Phen and the ⁵D₁→⁵D₀ energy transfer path within Eu³⁺ ion. Both luminescence spectra and crystal structure lead to the conclusion that the local symmetry around the Eu³⁺ ion is C₁ and that more than one Eu³⁺ ion sites having slight environmental difference are present.     

含能配位聚合物[Co4(HBTI)4(H2O)8]的合成、结构、爆轰性能及催化性质

我们以4,5-双四唑咪唑（H₃BTI）为能量配体,利用水热法构筑了一例新型含能配合物[Co₄（HBTI）₄（H₂O）₈]（1）。晶体结构测定表明配合物1呈中心对称的四核结构,中心离子Co（Ⅱ）呈六配位的八面体几何构型。此外,结合Kissinger和Ozawa-Doyle两种方法对1进行非等温热动力学分析,并基于密度泛函理论计算出1的爆轰性能相关参数。配合物1的摩擦感度高于360 N,且撞击感度高于40 J。配合物1可同时催化高氯酸铵（AP）和1,3,5-三硝基-1,3,5-三嗪烷（RDX）的燃烧分解反应,其分解温度分别提前了25和11℃。     

含能配位聚合物[Co4(HBTI)4(H2O)8]的合成、结构、爆轰性能及催化性质

我们以4,5-双四唑咪唑(H₃BTI)为能量配体,利用水热法构筑了一例新型含能配合物[Co₄(HBTI)₄(H₂O)₈](1)。晶体结构测定表明配合物1呈中心对称的四核结构,中心离子Co(Ⅱ)呈六配位的八面体几何构型。此外,结合Kissinger和Ozawa-Doyle两种方法对1进行非等温热动力学分析,并基于密度泛函理论计算出1的爆轰性能相关参数。配合物1的摩擦感度高于360 N,且撞击感度高于40 J。配合物1可同时催化高氯酸铵(AP)和1,3,5-三硝基-1,3,5-三嗪烷(RDX)的燃烧分解反应,其分解温度分别提前了25和11℃。     

一维交替链状稀土配位聚合物[Er(dpa)(pya)(H2O)]n和[Nd2(pya)6(H2O)4]n的水热合成及结构表征

在水热条件下，稀土氧化物与2，2′-联苯二甲酸及异烟酸反应得到了两个新颖的一维交替链状配位聚合物[Er(dpa)(pya)(H₂O)]_n和[Nd₂(pya)₆(H₂O)₄]_n(H₂dpa=2，2′-联苯二甲酸；Hpya=异烟酸)。测定了它们的晶体结构，并进行了红外光谱和元素分析等 性质的表征。晶体结构测定表明这两个化合物同属单斜晶系，并具有相同的空间群P2₁/n， 晶体学参数分别为配合物1：a= 0.8830(3) nm，b=1.058 5(3) nm，c=2.089 1(6) nm，β=98.429(4)°，D_c=1.883g·cm^-3， V=1.931 4(10) nm³，Z=4； 配合物2：a=0.968 9(4) nm，b=1.978 3(9) nm，c=1.164 2(6) nm，β=112.106(7)°，D_c=1.756 g·cm^-3，V=2.067 5(17) nm³，Z=4。     

三维多孔配位聚合物{[Zn2(mal)2(4,4'-bipy)(H2O)2]•2(H2O)0.25}∞ (mal＝丙二酸根)的合成、结构及性质研究

ZnO, 丙二酸及4,4'-bipy按物质的量之比1∶3∶0.3溶于H₂O和DMF混合溶剂中(体积比4∶1), 形成的无色溶液在50 ℃反应 3 d, 得到了标题化合物{[Zn₂(mal)₂(4,4'-bipy)(H₂O)₂]•2(H₂O)_0.25}_∞ (mal＝丙二酸根), 对其进行了元素分析、红外光谱和X射线衍射表征, 测定了晶体结构. 该聚合物属单斜晶系, P2₁/n空间群, a＝0.71215(16) nm, b＝1.8685(4) nm, c＝0.73890(17) nm, β＝91.486(5)°, V＝0.9829(4) nm³, Z＝4, D_c＝1.811 g/cm³, M_r＝268.03, F(000)＝542, μ＝25.02 cm^－1. 最终偏离因子R₁＝0.0499, wR₂＝0.1374. 该化合物中Zn原子和三个丙二酸根中的4个O原子、一个水分子和4,4'-bipy的一个N原子配位, 形成的ZnNO₅八面体通过4,4'-bipy和丙二酸根桥联, 组成一种新颖的三维多孔结构, 其孔道中充填游离水分子. 此外还研究了该聚合物的热性质.     

Crystal structure and magnetic property of spin crossover complex Fe(3-phenylpyridine)2[Au(CN)2]2

A novel two-dimensional network bimetallic Fe Au spin crossover coordination polymer based on 3-phenylpyridine-coordinated iron centers and linear gold cyanide bridges {Fe(3-phenylpyridine)₂[Au(CN)₂]₂}_n (1), has been synthesized. The compound is characterized by elemental analysis, IR, single-crystal X-ray analysis at 300 and 90 K and magnetic measurements. The Fe^II ions in 1 have octahedral Fe^IIN₆ coordination geometries, which are linked by [Au(CN)₂]⁻ units at the equatorial plane to form a polymeric 2D sheet architecture. The two pyridine rings coordinate in axial position. Variable-temperature (2-300 K) magnetic susceptibility measurements of 1 were performed to determine the spin transition behavior. SQUID data show that high and low spin states exist in a 1:1 ratio at 90 K. However, only one kind of Fe^II atom is apparent crystallographically at 90 K, indicating that the high and low spin sites are disordered in the polymeric 2D framework.     

Nuclear magnetic resonance for differentiating two inequivalent M sites in double anhydrous M2CuCl4 (M = K,Cs, and NH4) single crystals

Nuclear magnetic resonance (NMR) spectra and the spin-lattice relaxation times (T₁) for the M nuclei (M = K, Cs, and NH₄) in M₂CuCl₄ crystals were studied as functions of temperature. The K₂CuCl₄, Cs₂CuCl₄, and (NH₄)₂CuCl₄ single crystals all have the same M₂BX₄ structure, and their two inequivalent sites M(1) and M(2) were differentiated using the NMR results. Because M(2) is surrounded by fewer but closer Cl ligands than M(1), it has a shorter T₁ value than M(1). However, the three crystals have different T₁ temperature dependences and dynamic properties. The rotational tumbling motion defined by the Bloembergen-Purcell-Pound theory was found to occur in (NH₄)₂CuCl₄, but not in K₂CuCl₄ or Cs₂CuCl₄. The differences observed in the spin-lattice relaxation times of the M nuclei may be related to their ionic masses.     

Synthesis, characterization, properties and crystal structure of heterometallic 1D coordination polymers {[CuLZn·CuLZn(H2O)]·H2O}n

Copper-zinc heterometallic 1D chain coordination polymer has been synthesized and characterized by elemental analysis, and IR spectra etc. The crystal structure was determined by single-crystal X-ray diffraction analyses. The title complex is 1D chain coordination polymer with the chemical formula {[CuLZn·CuLZn(H₂O)]·H₂O}_n, where H₄L=N-(2-hydroxybenzamido)-N′-(3-carboxylsalicylidene)ethylenediamine. Its structural unit is comprosed of two tetranuclear cycles formed by two dissymmetrical tetranuclear units. These units polymerized each other to form 1D chain coordination polymer.     

[Pb2(TNR)2(CHZ)2(H2O)2]4H2O的结构及热分解机理

The coordination compound of [Pb 2(TNR) 2(CHZ) 2(H 2O) 2]•4H 2O was prepared by using the aqueous solution of carbohydrazide, lead nitrate and sodium styphnate. The molecular structure of [Pb 2(TNR) 2(CHZ) 2(H 2O) 2]•4H 2O(C 7H 13 N 7O 12 Pb, Mr=594.43) was determined by using a single crystal diffraction analysis .The thermal decomposition mechanism of the title compound was studied by TGDTG, DSC and IR techniques. The crystal belongs to monoclinic with space group P2 1/n.The unit cell parameters are as follows: a=0.64700(10)nm, b=1.6074(3)nm, c=1.4883(3)nm,β=97.42(2)°,V=1.5349(5)nm3, Z=2, DC=2.572g•cm -3 ,μ(Mo, Kα)=11.080cm -1 , F(000)=1128. R=0.0422, Rw=0.0735. The binuclear lead coordination compound is bridged by two carbohydrazide molecules. The molecule has a symmetrical center. TNR 2- ,CHZ and H 2O coordinate with the central ions simultaneously.     

氢键构筑的新颖微孔配位聚合物[Co2(Hisor)2·(4,4′-bpy)2(H2O)2]·4,4′-bpy的合成与结构

A novel microporous coordination polymer [Co2(Hisor)2(4,4′-bpy)2(H2O)2]·4,4′-bpy was synthesized by hydrothermal reaction and characterized by single crystal X-ray diffraction, elemental analysis and IR spectrum. The crystal belongs to the monoclinic system and space group is P2/n with a=1.040 6(3) nm, b=1.138 8(4) nm, c=1.854 7(6) nm, β=102.991(6)°, V= 2.141 6(12) nm3, Z=2, Dc=1.443 Mg/m3, Mr=930.62, μ=0.842 mm-1, F(000)=952, GOF= 1.072, R=0.065 4, wR=0.146 8[I>2σ(I)]. There are two crystallographically independent Co(Ⅱ) ions in the title complex. The Hisor2- and 4,4′-bpy link the metal ions into 2D grids with dimension of 0.522 3 nm×1.138 8 nm. There are O—H…O and N—H…O hydrogen bonds in the complex resulting in the formation of 3D network with 1D channels, in which are free 4,4′-bpy molecules.     

两个具stp三维拓扑构型的稀土配位聚合物{[Ln2（pda）3（H2O）2]2H2O}n（Ln=Nd/La）

本文利用水热合成方法,将稀土氧化物与邻苯二乙酸（H₂pda）反应得到了2个新颖的稀土配位聚合物{[Ln₂（pda）₃（H₂O）₂]·2H₂O}_n（Ln=Nd（1）,La（2））。测定了它们的晶体结构,并进行了X-射线单晶衍射、红外光谱、荧光光谱和热重分析等性质的表征。晶体结构测定表明这2个化合物为异质同晶化合物。属单斜晶系,C2/c空间群。晶体学参数分别为配合物1：a=2.62906（18）nm,b=1.61172（11）nm,c=0.78327（5）nm,β=93.173（5）°,V=3.3139（4）nm³,Z=4,F（000）=1840,μ=3.173mm^-1,D_c=1.878g·cm^-3,R₁=0.0226,wR₂=0.0609;配合物2：a=2.6271（14）nm,b=1.6149（8）nm,c=0.7966（4）nm,β=92.850（9）,V=3.375（3）nm³,Z=4,F（000）=1816,μ=2.570mm^-1,D_c=1.823g·cm^-3,R₁=0.0466,wR₂=0.1416。化合物中邻苯二乙酸配体连接相邻的稀土金属离子,形成复杂的具有stp拓朴构型的三维网络结构。     

Synthesis,crystal structure and catalytic activity for H2O2 disproportionation of the manganese(II) coordination polymer {[Mn(O2C(CF2)8CO2)(phen)2]H2O}n (phen = 1,10-phenanthroline)

The title polymeric complex {[Mn(O₂C(CF₂)₈CO₂)(phen)₂]H₂O}_n was synthesized through the reaction of 1,10-phenanthroline, perfluorosebacic acid and MnCO₃ · H₂O. The molecular structure was characterized by X-ray diffraction, elemental analysis, thermal gravimetry, IR and UV–Vis spectroscopy and its catalytic activity has been studied. X-ray structure analysis shows that each Mn(II) ion is octahedrally coordinated by two bidentate phenanthroline ligands and the carboxylate oxygen atoms from two symmetry related perfluorosebacate ligands, which are coordinated in cisoid positions. The structure consists of polymeric chains, with the perfluorosebacato ligand bridging the Mn(II) ions in a monodentate fashion. Crystallographic characterization shows a supramolecular structure involving hydrogen bonds, π–π and π-ring interactions. The catalytic results indicated that the complex has reasonably good activity towards the disproportionation of hydrogen peroxide into water and dioxygen in methanol and it does not exhibit saturation kinetics with the substrate. The initial reaction rates and their temperature and base dependencies were investigated by monitoring the dioxygen evolution. Kinetic studies revealed a first-order dependence on the catalyst concentration. Activation parameters have been calculated at 301 K.     

A family of three-dimensional porous coordination polymers with general formula (Kat)2[{M(H2O)n}3{Re6Q8(CN)6}2]·xH2O (Q=S, Se; n=1.5, 2)

The X-ray crystal structures of a series of new compounds (H₃O)₂[{Mn(H₂O)_1.5}₃{Re₆Se₈(CN)₆}₂]·19H₂O (1), (Me₄N)₂[{Co(H₂O)_1.5}₃{Re₆S₈(CN)₆}₂]·13H₂O (2), (Me₄N)₂[{Co(H₂O)_1.5}₃{Re₆Se₈(CN)₆}₂]·3H₂O (3), (Et₄N)₂[{Mn(H₂O)₂}₃{Re₆Se₈(CN)₆}₂]·6.5H₂O (4), (Et₄N)₂[{Ni(H₂O)₂}₃{Re₆S₈(CN)₆}₂]·6.5H₂O (5), and (Et₄N)₂[{Co(H₂O)₂}₃{Re₆S₈(CN)₆}₂]·10H₂O (6) are reported. All six compounds are isostructural crystallizing in cubic space group with four formulae per unit cell. For compounds 1, 3-5 the following parameters were found: (1) a=19.857(2) Å, R1=0.0283; (3 at 150 K) a=19.634(1) Å, R1=0.0572; (4) a=20.060(2) Å, R1=0.0288; (5) a=19.697(2) Å, R1=0.0224. The structures consist three-dimensional cyano-bridged framework formed by cyano cluster anions [Re₆Q₈(CN)₆]⁴⁻, Q=S, Se and transition metal cations, M²⁺=Mn²⁺, Co²⁺, Ni²⁺. Water molecules and large organic cations Me₄N⁺ and Et₄N⁺ are included in cavities of this framework. Porosity of the framework, its ability to accommodate different cations and water molecules by little changes in the structure, as well as distortion of coordination framework under loss of water of crystallization is discussed.     

Co3{CH3C(NH3)(PO3H)(PO3)}2 {CH3C(NH3)(PO3H)2}2(H2O)4·2H2O: A cobalt 1-aminoethylidenediphosphonate with a layer structure

This paper describes the structure and magnetic properties of a novel cobalt 1-aminoethylidenediphosphonate compound, namely Co₃{CH₃C(NH₃)(PO₃H)(PO₃)}₂{CH₃C(NH₃)(PO₃H)₂}₂(H₂O)₄·2H₂O (1). The structure contains a trimer unit of Co₃{CH₃C(NH₃)(PO₃H)(PO₃)}₂ in which two equivalent phosphonate ligands chelate and bridge the three cobalt ions. Each trimer unit is further linked to its four equivalent neighbors through corner-sharing of CoO₆ octahedra and CPO₃ tetrahedra, forming a two-dimensional layer in the bc-plane which contains 12-membered rings. These layers are connected to each other by extensive hydrogen bonds. Magnetic studies show that weak antiferromagnetic interactions are mediated between the cobalt ions. Crystal data for 1: monoclinic, space group C2/c, a=27.727(4), b=7.1091(11), , β=118.488(3), , Z=2.     

A single-helix coordination polymer with mixed ligands [Zn2(phen)2(e,a-cis-1,4-chdc)2(H2O)2]n (phen=1,10-phenanthroline; chdc=cyclohexanedicarboxylate)

A coordination polymer with mixed ligands [Zn₂(phen)₂(e,a-cis-1,4-chdc)₂(H₂O)₂]_n (chdc=cyclohexanedicarboxylic acid; phen=1,10-phenanthroline) was prepared under hydrothermal conditions and characterized by elemental analyses, IR spectra, TG analysis, and single-crystal X-ray diffraction analysis. X-ray crystal structural analyses reveal that 1 and 2 are isomorphic and belong to the monoclinic system. C₄₀H₃₆Zn₂N₄O₁₀, P2₁/c, a=10.084(2) Å, b=8.9072(18) Å, c=20.276(4) Å, β=99.92(3)°, V=1793.9(6) Å³, Z=1. In the structures of 1, the 1,4-chdc ligand possesses only one kind of e,a-cis-conformation although there are both cis- and trans-conformations in the raw material. Two oxygen atoms of one carboxyl in 1,4-chdc ligand and another oxygen atom of contraposition carboxyl link adjacent Zn atoms into an infinite 1D zigzag chain. The most attractive structural feature of 1 is that it exhibits an infinite chiral chain-like structure with 2₁ helices along the b-axis. In addition, the right- and left-handed chains are alternate. Meanwhile, the adjacent chains of 1 is linked via hydrogen bonds into 2D network structures, which further form 3D frameworks via π-π interactions of 1,10-phen.     

具有双螺旋链的新型镉(II)大豆甙元衍生物配位聚合物[Cd(L)(H2O)3]•2H2O的合成与晶体结构研究

合成新型大豆甙元衍生物Cd(II)配合物[Cd(L)(H₂O)₃]•2H₂O (H₂L＝3'-磺酸钠-4'-羟基-7-羧甲基异黄酮), 采用单晶X射线衍射、元素分析和IR对其进行表征. 该配合物属单斜晶系, 空间群为P2₁/a, 晶胞参数a＝1.3691(3) nm, b＝0.72157(16) nm, c＝2.0163(5) nm, α＝90°, β＝93.501(4)°, γ＝90°, V＝1.9882(8) nm³, M_r＝592.79, Z＝4, D_c＝1.980 g•cm^－3, F(000)＝1192, μ＝1.283 mm^－1, R₁＝0.0387, wR₂＝0.1224. X射线单晶衍射分析结果表明, 该单晶中Cd(II)为六配位, 它除了与配体L中羧基和磺酸基上的氧原子配位外, 还与溶剂中的3个水分子发生配位, 形成了以Cd(II)为中心的八面体配位构型. 该晶体结构中存在着平行于b轴的双螺旋链, 左手螺旋Cd-L链和右手螺旋Cd-L链的交替排列构成了二维层状结构. 由于配位水和晶格水以及配体中CO₂, SO₃, O, CO, OH等的存在, 该晶体中存在着丰富而复杂的氢键, 二维层状结构之间依靠这些复杂的氢键作用形成三维超分子结构.     

Crystal structure of a new coordination polymer [LaAg(Pydc)(HPydc)(C2O4)0.5(H2O)2]n (H2Pydc = pyridine-3,5-dicarboxylic acid)

A new 3D coordination polymer, [LaAg(Pydc)(HPydc)(C₂O₄)_0.5(H₂O)₂] _n (I) (H₂Pydc = pyridine-3,5-dicarboxylic acid), has been hydrothermally synthesized and characterized by elemental analyses and single crystal X-ray diffraction. The X-ray diffraction analysis reveals that I (C₁₅H₁₁AgLaN₂O₁₂) crystallizes in triclinic space group P $ \bar 1 $ \bar 1 and features an interesting 3D framework constructed by 2D layers via strong Ag-Ag interactions. Unit cell parameters for I (n = 1): a = 7.749(2), b = 8.316(1), c = 14.239(3) ?, α = 97.64(2)°, β = 100.12(2)°, γ = 94.37(2)°, and Z = 2.     

Crystal structure of new hydroxide fluorides with isolated F anions: [H3N(CH2)6NH3]2M(F, OH)6(F,OH)·H2O (M = Al, In)

The synthesis and structural characterization of new hydroxo-fluorometallates [H₃N(CH₂)₆NH₃]₂M(F,OH)₇·H₂O (M=Al, In) are presented. Their preparation is achieved in solvothermal conditions by microwave or classical heating. The isotopic structures, determined by single crystal X-ray diffraction, are triclinic with the space group P–1. The structural arrangement can be described from isolated MX₆ (X=F, OH) octahedra connected by diprotonated diaminohexane via a complex network of hydrogen bonds. X⁻ anions and water molecules are found between the organic chains. A study by ¹⁹F NMR of the Al compound confirms a statistical occupancy of fluorine sites by hydroxyl groups and the occurrence of isolated F⁻ anions.     

Preparation, crystal structure and magnetic properties of Ni2(dpa)2(pyz)(H2O)4

A Ni(II)-based dimer structure, Ni₂(dpa)₂(pyz)(H₂O)₄ (dpa = 2,6-pyridine dicarboxylic acid dianion, pyz: pyrazine), has been prepared using hydrothermal synthesis and the solid-state magnetic properties have been evaluated. In the dimeric structure, the planar tridentate 2,6-pyridine dicarboxylic acid dianion coordinates to a Ni(II) ion in a meridional fashion and defines the equatorial plane of the complex. The fourth equatorial coordination site is then occupied by a pyrazine molecule that functions as a linear bidentate ligand bridging two Ni(II) complexes to form a dimer. The axial positions of each Ni(II) complex are occupied by two water molecules to form a distorted octahedral geometry. Susceptibility and magnetization measurements show that both intra-dimer and inter-dimer exchange interactions are weakly antiferromagnetic. The fitting of the magnetic data also indicates the existence of a large axial zero-field splitting term that contributes to the small magnetization even under high fields.