Synthesis,Crystal Structure and Thermal Stability Properties of a Binuclear Copper(Ⅱ) Coordination Polymer {[Cu_2(4,4'-bipy)_2(o-ABA)_4(H_2O)_2][(H_2O)_2]}_n

One-dimensional chain copper（Ⅱ） coordination polymer has been synthesized and characterized in the solvent mixture of water and alcohol with o-acetamidobenzoic acid,4,4＇-bipyridine and copper perchlorate.It is of tetragonal,space group P41212 with a=1.57756（10）,b= 1.57756（10）,c=2.1438（3）nm,V=5.3352（8） nm^3,Dc=1.524 g/cm^3,Z=4,F（000）=2536,R= 0.0479 and wR=0.0979.The crystal structure shows two coordination modes.The copper（1） is coordinated with two nitrogen atoms of one 4,4＇-bipyridine molecule and two oxygen atoms from two o-acetamidobenzoic acid molecules,forming a distorted tetrahedral coordination geometry; the copper（2） is coordinated with two nitrogen atoms of one 4,4＇-bipyridine molecule,four oxygen atoms from two o-acetamidobenzoic acid molecules and two water molecules,generating a distorted octahedral coordination geometry.The result of TG analysis shows that the title complex is stable below 180.0 ℃.

Hydrothermal Synthesis and Crystal Structure of a Manganese(II) Coordination Polymer with 1,1′-Biphenyl-2,2′,6,6′-tetracarboxyl Acid and 2,2′:6,2′′-Terpyridine Ligands

The title compound {[Mn（H2BPTC）（tpy）（H2O）]·（H2O）3}, （1, H4BPTC = 1,1＇- biphenyl-2,2＇,6,6＇-tetracarboxylic acid, tby = 2,2＇：6,2＇-terpyridine） has been synthesized by the hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of monoclinic, space group P21/c with a = 10.971（2）, b = 20.776（4）, c = 14.332（3） A, β = 109.25（3）°, MnC31H27N3O12, Mr = 688.50, V= 3084.1（10） A^3, Dc = 1.483 g/cm^3, F（000） = 1420, p = 0.498 mm^-1, S = 1.066 and Z = 4. The final refinement gave R = 0.0447 and wR = 0.1103 for 5107 observed reflections with I 〉 2σ（I）. The title complex has a {[Mn（H2BPTC）（tpy）（H2O）]}, chain structure, and the hydrogen bonding interactions make it more stable. Each chain is further connected to the adjacent ones through π…π, C-H…π and rich hydrogen bonds to form a metal-organic coordination polymer.

A 2D Brickwall-like Copper(Ⅱ) Coordination Polymer Based on Phenyliminodiacetate and 4,4?-Bipyridine: Synthesis,Crystal Structure and Magnetic Property

A novel copper（II） coordination polymer of {[Cu3L2（4,4＂-bipy）4]（CIO4）2＂20H20}, （1） was synthesized by the reaction of H2L （C6HsN（CH2COOH）2, phenyliminodiacetic acid）, CuSO4.5H20, NaCIO4.H20 and 4,4＂-bipy （4,4＂-bipyridine） in water/methanol, followed by slow evaporating at room temperature. The compound was characterized by elemental analysis （EA）, infrared spectroscopy （IR）, thermogravimetric analysis （TGA） and single-crystal/powder X-ray diffraction. The result of single-crystal X-ray diffraction analysis reveals that 1 crystallizes in the monoclinic crystal system with C2/c space group, a = 2.9974（4）, b = 1.7270（2）, c = 2.0007（3） nm, fl = 128.793（2）°, V= 8.0722（19） nm3, Z = 4, Dc = 1.472 g.cm-3,/a = 0.942 mm-1, F（000） = 3716, R= 0.0487 and wR = 0.1204 （I 〉 20（/））. The basic structural unit of 1 is a trinuclear cluster unit of [Cu3L2]2＋, which is constructed by two #2-L2- ligands bridging and chelating three Cu（Ⅱ） ions. These [Cu3L2]2＋ units are connected with each other by 4,4＂-bipy ligands to generate a 2D cation brickwall-like network of [Cu3L2（4,4＂-bipy）4]n2n＋. These adjacent 2D cation layers are further stacked in a staggered fashion via interlayer stacking interactions to form a 3D supramolecular structure with 1D open square channels, in which the C104- counter anions and lattice water molecules are filled. Furthermore, the magnetic property of 1 was also investigated.

Synthesis, Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn(NAA)_2(4,4’-bipy)(H_2O)_4]_n

A novel one-dimensional chain coordination polymer [Mn（NAAh（4,4′-bipy）（H2O）4], has been synthesized with a-naphthaleneacetic acid, 4,4′-bipy and manganese（Ⅱ） sulfate as raw materials. Crystal data for this complex： monoclinic, space group P21/c, a = 1.1421（2）, b = 1.6337（3）, c = 0.94177（19） nm, β = 112.15（3）°, V = 1.6275（6） nm^3, De = 1.407 g/cm^3, Z = 2, μ（MoKa） = 0.467 mm^-1, F（000） = 722, S = 1.007, R= 0.0412 and wR = 0.1022. The crystal structure shows that two neighboring manganese（Ⅱ） ions are linked together by one 4,4′-bipy molecule, and the whole complex molecule forms a one-dimensional chain structure. Each manganese（Ⅱ） ion is coordinated with two oxygen atoms of two a-naphthaleneacetic acid molecules, two nitrogen atoms of two 4,4′-bipy molecules and two oxygen atoms from two water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were also analyzed.

Synthesis, Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn(phen)(2,4,6-TMBA)_2(H_2O)]_n

A one-dimensional chain-like coordination polymer [Mn（phen）（2,4,6-TMBA）2（H2O）]n has been synthesized from 2,4,6-trimethylbenzoic acid, 1,10-phenanthroline and anhydrous manganese（Ⅱ ） sulfate and then characterized. Crystal data for this complex： tetragonal, space group I41, a = 2.05643（16）, b = 2.05643（16）, c = 1.3939（2） nm, V = 5.8946（11） nm^3, Mr = 579.54, Z = 8, Dc = 1.306 g/cm^3, μ（MoKα） = 0.490 mm^-1, F（000） = 2424, S = 0.985, the final R = 0.0411 and wR = 0.0950. The Flack factor is -0.01（2）. The crystal structure shows that two neighboring man- ganese（Ⅱ ） ions are linked together by one bridge-chelating 2,4,6-trimethylbenzoic group, forming a one-dimensional chain structure. The manganese（Ⅱ ） ion is coordinated with two nitrogen atoms of one 1,10-phenanthroline, three oxygen atoms from three 2,4,6-trimethylbenzoic acids and one water oxygen atom, giving a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex was also investigated.

Synthesis and Crystal Structure of a 1-D Coordination Polymer {[Cu(NIT4py)_2(ip)]·6H_2O}_n

A new complex { [Cu（NIT4py）2（ip）]·6H2O }, （NIT4py=2-（4＂-pyridinyl）-4,4,5,5-tetra methylimidazoline-1-oxyl-3-oxide and ip = isophthalate dianion） has been synthesized and structurally characterized by X-ray diffraction. It crystallizes in orthorhombic, space group Cmcm with a = 25.161（3）, b =10.045（1）, c = 15.450（2） A°, C32H48N6O14CU, Mr = 804.30, V= 3904.8（8） ,A°^3, Z = 4, De = 1.368 g/cm^3, μ（MoKa） = 0.630 mm^-1, F（000） = 1692, the final R = 0.0326 and wR = 0.0787 for 1843 independent reflections with Rint = 0.0372. Each Cu（Ⅱ） ion is four-coordinated by two carboxylate oxygen atoms and two pyridyl-N atoms from NIT4py radicals to furnish a rhombus geometry. The central Cu（Ⅱ） ion is located at an inversion center and a crystallographic two-fold axis. Each isophthalate dianion binds two Cu（Ⅱ） ions in bis-monodentate mode, leading to a 1-D chain, a＇ these 1-D chains are further linked into a 2-D network via hydrogen-bonding interactions.

Hydrothermal Synthesis and Crystal Structure of a New 2D Mn(II) Coordination Polymer with 4,4′-Sulfonyldi Benzoic Acid and 1,4-Bis(imidazol-1-ylmethyl) benzene Ligands

A novel manganese coordination polymer [Mn2（sfdb）2（biyb）2（H2O）2]n （1, H2sfdb = 4,4′-sulfonyldibenzoic acid, biyb = 1,4-bis（imidazol-1-ylmethyl）benze） has been hydrothermally synthesized and structurally characterized by single-crystal X-ray determination, IR and thermogravimetric analysis （TGA）. Complex 1 crystallizes in the triclinic system, space group Pi with a = 10.138（4）, b = 11.187（5）, c = 13.582（6） A, α = 69.146（7）, β = 89.628（7）, γ = 77.076（7）°, MnzC56H48N8O14S2, Mr= 1231.02, V= 1398.5（10） A3, Dc= 1.462 g/cm3, F（000） = 634,μ = 0.600 mm-1, S = 1.088 and Z = 1. The final refinement gave R = 0.0570 and wR = 0.1229 for 4889 observed reflections with 1 〉 2σ（I）. Interestingly, in complex 1, the sfdb2 and biyb ligands connect the Mn（Ⅱ） ions into two-dimensional 2-fold interpenetrating layers, and such layers are further connected with each other to generate a 3D supramolecular structure through hydrogen bonding interaction.

Crystal Structure, Thermal Behavior and Luminescence of a New Copper Coordination Polymer Constructed with 4-(Carboxymethoxy)-benzoic Acid

A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallographic data for 1: triclinic, space group P1 with a = 9.750(5), b = 10.148(5), c = 12.869(5) ?, α = 104.904(5), β = 102.133(5), γ = 95.219(5)°, V = 1188.7(10) ?~3, Z = 2, C_(28)H_(17)FN_4O_5Cu, Mr = 572.01, D_c = 1.598 g/cm^3, F(000) = 582, μ(MoKa) = 0.977 mm^(-1), R = 0.0474 and w R = 0.1144. The TGA behaviors and luminescence of 1 have been studied in detail. The L1 dianions link neighboring Cu(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L2 ligands are attached on one side of the chain through chelating the Cu(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. Additionally, the N–H???O hydrogen bonds further stabilize the structure of 1.

Syntheses, Structures and Properties of Two 2D Coordination Polymers from 5-(Pyridin-2-yl-methyl)aminoisophthalate

Hydrothermal reactions of 5-（pyridin-2-yl-methyl）aminoisophthalic acid（H2paip） with Mn（OAc）2·4H2O and Cu（NO3）2·3H2O produced two 2D complexes, [Mn（paip）]n·nH2O（1） and [Cu（paip）（H2O）]n（2）. In complex 1, paip serves as a μ4-bridge, and its two carboxylate groups in μ2,η2-bridging and chelating modes connect Mn（Ⅱ） into 1D chains, which are further extended into a 2D layer through coordination of two chelating nitrogen atoms. However, paip in complex 2 acts as a μ3-bridge to link Cu（Ⅱ） into a 2D layer, in which two carboxylate groups function in a monodentate mode, and hydrogen bonds between the coordinated water and carboxylate oxygen atoms further extend the 2D layers into a 3D supramolecular network. The frameworks of complexes 1 and 2 are stable up to 470 and 250 ℃, respectively. Magnetic measurement shows that complex 2 possesses a weak antiferromagnetic interaction.

Synthesis,Structure and Property of a 1D Coordination Polymer [Mn{5-(NO_2)sal}2_(phen)]_n with 5-Nitrosalicylate Ligand

A new coordination polymer [Mn{5-（NO2）sal}2（phen）]n （5-（NO2）sal = 5-nitrosalicylate, phen = 1,10-phenanthroline） was synthesized by a hydrothermal reaction and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The title complex crystallizes in orthorhombic, space group Pbcn with α = 25.747（8）, b = 13.220（4）, c = 7.009（3） A, V= 2386（1）A^3, Z = 4, R = 0.0427 and wR = 0.0890. The 5-nitrosalicylate anions doubly bridge the Mn（Ⅱ） atoms to form a one-dimensional polymeric chain with repeated eight-membered ring units （Mn-O-C-O）2. The crystal structure is stabilized by intra- and interchain hydrogen bonding interactions. The cyclic voltammetric behavior of the title complex is also reported.

Assembly and Crystal Structure of a Novel 1-D Coordination Polymer of Copper(II) with Thiocyanate and 4-Cyanopyridine

A novel one-dimensional coordination polymer, Catena-poly [bis(4-cyano-pyridyl) copper (Ⅱ) -di-thiocyanate], [Cu~Ⅱ-(cypy)_2(μN,s-SCN)_2] (cypy =4-cyano-pyridyl), was synthesized in a solution reaction of CuCNO_3)_2·3H_2O, 4-cyano-pyridine andKSCN in mole ratio of 1:2:2 at room temperature. Its crystal structure was determined bysingle-crystal X-ray diffraction. The crystal belongs to monoclinic crystal system, space groupP2_1/c with cell parameters a = 1.0719(2), b = 1.8441(4), c = 0.9144(2) nm, β = 110.49(3)° and Z =4. A full-matrix least-squares refinement gave R_1 = 0.0393 and wR_2 = 0.0916 for 1554 reflectionshaving I > 2σ (Ⅰ). The crystal is thermally stable up to approximately 170℃.

Anion Directed Assembly of Cu(Ⅱ)Complexes Formed by a Flexible Ligand

Coordination polymers,consisting of metal,anion and organic ligands,have attracted much attention.The structure of coordination polymers is affected by various factors.To investigate the effects of anion,syntheses and structures of four Cu(II)complexes,namely[(Cu LCl)(PF)](1),[(Cu LCl)(ClO)](2),[(Cu LCl)?CHOH](3)and Cu LCl(4),are reported based on a flexible ligand,1,3-bis(2-pyridylmethyl)imidazolium(L).The ligand is accommodative to kinds of anions,and forms 1-D chains generally upon reaction with Cu(II)salts.The effect is measured by the conformational variation through the dihedral angles between different aromatic rings of the ligand.In order to further investigate the effect of anion,a protonated sample of L,namely,LH(ClO)?HO(5)is also synthesized and structurally characterized,showing an intriguing hydrogen bonded helix.

一维链状配位聚合物[M(H_(2)bpb)(H_(2)O)_(4)](SO_(4)_(2)·6H_(2)O[M=Zn(Ⅱ),Cu(Ⅱ)]的合成及晶体结构表征

设计并合成了一个含吡啶基团的柔性配体:N,N'-Bis(3-pyridylmethyl)-1,4-benzenedimethylamine(bpb)。通过bpb与硫酸锌及硫酸铜反应得到了两个新型具有一维链状结构的配位聚合物:犤M(H2bpb)(H2O)4犦(SO4)2·6H2O犤M=Zn?1,Cu?2犦。X-射线晶体结构测定表明,这两个化合物均属三斜晶系,并具有相同的空间群P1珔,晶体学参数分别为配合物1:a=11.8055(12)?,b=11.8778(12)?,c=12.1840(13)?,α=80.763(2)°,β=71.982(2)°,γ=80.913(2)°;配合物2:a=11.7403(19)?,b=11.890(2)?,c=12.254(2)?,α=71.339(3)°,β=81.936(4)°,γ=80.917(4)°。

一个新型氰根桥联铁(Ⅲ)-铜(Ⅱ)大环配位聚合物的合成和晶体结构

合成了新型大环配位聚合物 [Cu(L) ]2 [Fe2 (H2 O) (CN) 10 ]·8H2 O(L =1,8-二正丙基- 1,3,6 ,8,10 ,13-六氮杂 - 14-冠 - 4 ) ,用元素分析、ICP分析、IR光谱对配合物进行了表征 ,X -射线衍射测定了其单晶结构 .结果表明 ,该晶体属正交晶系 ,Pddd空间群 ,a =1.8310 (4)nm ,b =2 .6 0 6 0 (5)nm ,c =3.16 80 (6 )nm ,α =β =γ =90° ,V =15.116 (5)nm3,Z =8,dc=1.0 85g/cm3,F(0 0 0 ) =52 0 0 ,R1=0 .10 2 4 ,WR2 =0 .2 6 57,GOF(F2 ) =0 .992 .该配合物结构中氰根桥联铁 (Ⅲ )和铜 (Ⅱ ) ,形成Fe -CN -Cu -NC -Fe一维链 ,链与链之间经由Fe-O(H2 O) -Fe而相互联结 ,形成相互交叉的网状结构 .铁和铜均形成 6配位畸变 8面体构型 .

一维链状铜(Ⅱ)配合物的合成及晶体结构表征(英文)

The 1D-chain polymer of [Cu(Ⅱ)3L3(H2O)]n, (H2L=3-(3,5-dichloro-2-hydroxybenzylid-eneamino)propanoic acid) has been synthesized by reaction of 3,5-dichlorosalicylaldehyde, β-alamine and copper nitrate in ethanol solution. The crystal structure was determined by X-ray diffraction method. The crystal structure belongs to mono-clinic system with space group C2/c and cell parameters: a=3.853 7(3) nm, b=0.777 38(18) nm, c=2.656 36(2) nm, β=116.924(2)° and V=7.095 4(17) nm3, Mr=998.85, Z=8, Dc=1.870 g·cm-3 and F(000)=3 992. The two Cu(Ⅱ) atoms are coordinated with four atoms from Schiff base, and another one is coordinated with five atoms. The square bridging links three metal centers through a novel μ-4,4,5 coordination model, which is further assembled into 1D chain coordination polymer. The 1D chain is further constructed a 3D network by strong O-H…O and C-H…O hydrogen bonds. The coordination polymer presents a good thermal stable property through the thermal analysis.

酒石酸根桥联的二维网状铜(Ⅱ)配位聚合物的合成和晶体结构

合成了(S,S)-酒石酸根桥联的二维网状铜(Ⅱ)配位聚合物(S,S)-{[Cu2(C4H4O6)2(H2O)2].4H2O}n.用X-射线单晶衍射法测定了该配位聚合物的晶体结构.晶体属单斜晶系,P21空间群,晶胞参数:a=0.837 0(2)nm,b=0.875 5(2)nm,c=1.212 7(3)nm,β=104.54(2)°,V=0.860 2(3)nm3,μ=2.569 mm-1,Z=2,Dc=2.051 mg/m3,F(000)=540,Gof=1.065,最终偏离因子R1=0.023 2,wR2=0.059 4.在(S,S)-{[Cu2(C4H4O6)2(H2O)2].4H2O}n配位聚合物中,每个配位中心Cu(Ⅱ)离子的配位数均为六,这六个配位原子构成一扭曲的八面体结构.配位聚合物分子是通过一个(S,S)-酒石酸根中两端羧基的桥联双齿配位作用而形成无限延伸的二维网状结构.在晶体的堆积中,氢键为主要驱动力.

二维层状铜(Ⅱ)配位聚合物[Cu(PAc)_2(μ-3-PyOH)_2]_n的合成、晶体结构及热稳定性研究

羟基吡啶不仅是一类有机和药物合成的重要中间体,而且它含有的氮和氧两种配位原子,被认为是一种潜在的构筑配位聚合物的组织基元,近年来在晶体工程学和超分子化学领域中引起极大的重视。目前，对以羟基吡啶为小分子桥联配体参与构建一维或多维配位聚合物的研究主要集中在邻-羟基吡啶及其共振衍生物，而对于3-羟基吡啶及其配合物的研究报道很少，特别是以3-羟基吡啶作为配体构筑的铜（Ⅱ）配合物的结构研究报道很少。

以2,2′-联吡啶-4,4′-二甲酸和2-甲基吡嗪[3,2-f:2′,3′-h]喹喔啉为配体的三维锰(Ⅱ)配位聚合物的合成、晶体结构和荧光性质(英文)

采用水热法合成了一个锰的配合物[Mn(bpydc)(Medpq)]n(1)(H2bpydc=2,2′-联吡啶-4,4′-二甲酸,Medpq=2-甲基吡嗪[3,2-f:2′,3′-h]喹喔啉),并利用元素分析、红外光谱、紫外可见光谱、热分析和X-射线单晶衍射对其结构进行了表征。单晶结构分析表明配合物1属于单斜晶系,Cc空间群,晶胞参数a=2.031 6(4)nm,b=1.564 5(3)nm,c=0.719 26(14)nm,β=103.97(3)°,V=2.218 5(8)nm3,Z=4。配合物1是一个锰(Ⅱ)离子经由bpydc2-连接形成的三维网络结构。配合物1的固体荧光光谱表明它具有很强的荧光性。应用Gaussian 03W程序,在HF/LANL2DZ水平上对标题化合物的自然键轨道(NBO)进行了分析,结果表明Mn(Ⅱ)与配位原子间的价键类型都属于共价键范畴。

一例镍(Ⅱ)配位聚合物的合成、结构与磁性研究

以苯并咪唑-5-羧酸(Hbimc)、己二酸(H_(2)hex)、硝酸镍为原料,采用水热法合成了一例镍配位聚合物[Ni_(2)(bimc)_(2)(hex)]·2H_(2)O。利用单晶X射线衍射仪测试了该配位聚合物的晶体结构,采用粉末衍射(XRD)、元素分析、红外、热重(TG)等表征了其结构,并进行了磁性测定。单晶结构解析表明,配位聚合物为单斜晶系,空间群为P2_(1)/c,具有二维层状结构。配位聚合物对热稳定,整个框架可以维持到380℃。磁学性质研究表明配位聚合物存在反铁磁相互作用。

一维链状锰配位聚合物[Mn(1,5-nds)(Him)_4]_n的合成、晶体结构及热稳定性研究(英文)

The synthesis,structural characterization and thermal behavior of a novel one-dimensional manganese (Ⅱ) complex of formula [Mn(1,5-nds)(Him)4]n [1,5-nds=naphthalene-1,5-disulfonate,Him=imidazole] is reported.The complex crystallizes in the triclinic system,space group P1,with a=0.835 42(13) nm,b=0.983 45(18) nm,c= 0.987 42(19) nm,α=60.523 0(10)°,β=97.748(2)°,γ=87.189(2)° and Z=2.The 1,5-nds ligand assumes the μ2 coordination mode and interlinks Mn(Ⅱ) ions into infinite one-dimensional chain structure along [111] direction,with the adjacent Mn…Mn distance being 1.144 99(12) nm.The chains are assembled into a three-dimensional supramolecular architecture via hydrogen bonds and C-H…π interactions.IR spectra and thermal analysis data are in agreement with the crystal structure.