Hydrothermal Synthesis and Crystal Structure of a New Three-dimensional Co（II） Coordination Polymer Based on 2,3-Thiophenedicarboxylic Acid

A new Co（ll） polymer [Co（tdc）（l,4-bimb）]n 1 （H2tdc = thiophene-2,3-dicarboxy- lic acid, 1,4-bimb -- 1,4-bis（imidazol-1 ＇-yl）butane） was synthesized under hydrothermal conditions The compound crystallizes in the monoclinic system, space group C2/c with a = 15.643（9）, b = 8.839（5）, c=12.952（7） A, β = 105.964（6）°, V= 1721.8（16） A3, Z = 4, Mr = 419.32, Dc= 1.618 Mg/m3,μ = 1.149 mm-1, F（000） = 860, the final R = 0.0243 and wR =0.0613 for 1460 observed reflections with I 〉 2σ（I）. The compound presents a three-dimensional （3D） network extended by both tdc2- anions and 1,4-bimb ligands in which the tdc2- anions employ a chelating coordination mode. From the topology point of view, the structure could be described as a 3D 4-connected 65.8 CdSO4-type net. Infrared spectroscopy, elemental analyses, thermogravimetric analysis and powder X-ray diffraction properties of 1 are also investigated.     

Synthesis and Crystal Structure of a New(6,3)-Connected Ni(Ⅱ) Coordination Polymer

The coordination polymer [Ni(dpa)(bpp)]n(H2dpa = 2,4'-biphenyl-dicarboxylic acid,bpp = 1,3-di(4-pyridyl)propane) was hydrothermally prepared and characterized by single-crystal X-ray diffraction,FTIR spectra,elemental analysis and thermal analysis.The crystal is of triclinic system,space group P1 with a = 12.516(5),b = 12.943(5),c = 15.130(5) ,α = 94.331(5),β = 91.827(5),γ = 108.382(5)°,C54H44N4Ni2O8,Mr = 497.18,V = 2315.3(15) 3,Dc = 1.426 g/cm3,F(000) = 1032,μ = 0.875 cm-1,Z = 2,the final R = 0.0496 and wR = 0.1100 for 5365 reflections with Ⅰ 2σ(Ⅰ).X-ray diffraction analysis reveals that the carboxylate group of 2,4'-diphenic acids acting as bridging ligands adopts two coordination modes:bis-mondentate and bidentate chelating.The compound exhibits a two-dimensional(6,3)-connected architecture.     

Synthesis,Structure and Properties of Two New Coordination Polymers Based on 4-[（8-Hydroxy-5-quinolinyl）azo]-benzenesulfonic Acid

Two new coordination polymers based on 4-[（8-hydroxy-5-quinolinyl）azo]-benzenesulfonic acid（H2L）,{[CdL（H2O）2]·H2O}n（1） and {[CdL（en）]·EtOH}n（2）（en=ethylenediamine）,were solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Compounds 1 and 2 exhibit infinite 1D ladder-shaped chain structures,which are isostructural except that the two coordinating water molecules in compound 1 were replaced by one en molecule in compound 2 due to the use of different organic base.Compounds 1 and 2 were constructed into different supramolecular frameworks by hydrogen bonding and π…π stacking interactions.In addition,the fluorescent properties of compounds 1 and 2 were investigated.Furthermore,they were also investigated via IR spectral analysis,elemental analysis,powder X-ray diffraction（PXRD） and thermogravimetric analysis（TGA）.     

Two New Coordination Polymers Assembled with a Functionalized Ligand：Syntheses and Crystal Structures

Two new transition-metal organic coordination polymers [M(mna)2](M = Cd(1),Zn(2);mna = 2-mercaptonicotinic anion) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction along with IR and elemental analyses.Compound 1 is generally a one-dimensional linear structure bridged through the sulfur donor of mna ligand,while 2 is a one-dimensional zigzag chain ligated via the oxygen donor of mna ligand.These compounds further result in three-dimensional structures via intermolecular π...π stacking interactions and/or hydrogen bonding interactions.The two compounds were structurally determined by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic space group P21/c with a = 3.730(3),b = 13.973(12),c = 12.380(11) ,β = 97.953(18)°,V = 639.0(10) 3,Z = 2,CdC12H8O4N2S2,Mr = 420.72,Dc = 2.187 g/cm3,F(000) = 412,Rint = 0.0252,T = 293(2) K,μ = 2.052 mm?1,the final R = 0.0269 and wR = 0.0586 for 1377 observed reflections with I > 2σ(I).Complex 2 belongs to monoclinic space group P21/c with a = 13.376(2),b = 12.8429(14),c = 7.4856(10) ,β = 96.190(10)°,V = 1278.5(3) 3,Z = 4,ZnC12H8O4N2S2,Mr = 373.69,Dc = 1.941 g/cm3,F(000) = 752,Rint = 0.0414,T = 293(2) K,μ = 2.264 mm?1,the final R = 0.0418 and wR = 0.0966 for 2396 observed reflections with I > 2σ(I).     

Synthesis, Crystal Structure and Luminescence Property of a 2D Mn（II） Coordination Polymer Based on Isoniazid

A novel 2D Mn(Ⅱ) coordination polymer [Mn(CH3COO)2(INH)]n(INH=isoniazid) has been synthesized in DMF solution with isoniazid and Mn(CH3COO)2 . The polymer was characterized by single-crystal X-ray diffraction analysis, FTIR and X-ray powder diffraction (XRPD). The crystal belongs to the monoclinic system, space group P2 1 /c with a=9.3251(18), b=16.340(3), c=8.8096(17) , β=94.747(3)°, V=1337.7(4) 3 , Z=4, μ(MoKα)=1.006 mm -1 , F(000)=636, R=0.0754 and wR=0.1375 (I > 2σ(I)). In the complex, each Mn(Ⅱ) atom is coordinated to three CH3COO- groups and two INH ligands. The Mn(Ⅱ) atoms locate in a distorted coordination octahedron and are bridged by CH3COO- ions to form a 1D S shaped chain extending along the c direction. The INH molecules act as bridges to link the Mn(Ⅱ) atoms of adjacent chains and further construct a lamellar polymer. The remaining coordination site is occupied by an O atom of the other CH3COO-. The experimental results show that the title complex has good luminescence property and could be used as potential optical materials.     

Two Novel Zn（ll）-biphenyl-3,4,5-tricarboxylate Coordination Polymers： Syntheses,Crystal Structures and Luminescence Properties

Two novel Zn（II）-organic frameworks [（CH3）2NH2][Zn（BPT）]＇0.5DMF （1） and [Zn2（HBPT）2（1,4-bis）] （2） （H3BPT = biphenyl-3,4,5-tricarboxylic acid, 1,4-his = 1,4-bis（1H- imidazol-1-yl）butane） have been synthesized under solvothermal conditions, and characterized by IR spectroscopy, powder X-ray diffractions （PXRD） and single-crystal X-ray diffractions. Complex l displays a rtl rutile 3,6-connected network with {4.62}2{42.610.83} topology, while with the 1,4-his secondary ligand being introduced into the assembly, a different structure 2 has been obtained. Compound 2 forms a 2D layered framework through linking by both BPT and 1,4-bis ligands, which is further stacked via hydrogen-bonding interactions to a three-dimensional supramolecular architecture. Furthermore, thermal analyses （TGA） and photoluminescent properties of I and 2 are also investigated in detail.     

Syntheses,Structures,and Properties of Two New Coordination Polymers Based on Tetracarboxylate and 2,2′-Bipyridine Mixed Ligands

Two new coordination polymers {[Zn2L1(2,2'-bpy)2(H2O)2]·4H2O}n(1) and [Zn2L2(2,2'-bpy)2(H2O)2]n(2)(H4L1 = terphenyl-2,2',4,4'-tetracarboxylic acid, H4L2 = quarterphenyl-2,2',4,4'-tetracarboxylic acid, and 2,2'-bpy = 2,2'-bipyridine) have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction studies. Complex 1 displays 2D wavelike networks, which are further joined together through O–H···O hydrogen bonds to give a 3D supramolecular network. Complex 2 exhibits 1D ladder-like chains, and they are further joined together by π-π stacking and O–H···O hydrogen bonding interactions to form a 3D supramolecular network. The results indicate that the backbone of carboxylate ligands has significant effects on the formation and structure of the resulting functional coordination polymers. Additionally, thermal stability and photoluminescent properties of 1 and 2 are also investigated in detail.     

Synthesis and Crystal Structure of a Cu(Ⅱ) Coordination Polymer: [Cu(L)(1,10-phen)]_n

A new complex [Cu(L)(1,10-phen)]n(1, L = N-3-pyridine sulfonyl amino acid) has been synthesized and characterized by IR, elemental analysis and X-ray diffraction analysis, and its crystal belongs to monoclinic, space group P21/c with a = 11.481(2), b = 18.094(4), c = 8.5198(17) , β = 102.26(3)°,V = 1729.5(6) 3, Z = 4, Dc = 1.759 g/cm3, F(000) = 932, μ = 1.422 mm-1, R = 0.0368 and wR = 0.0893. In 1, the Cu(Ⅱ) ion adopts a slightly distorted five-coordinated square pyramidal geometry. The L2- ligand adopts O of the carboxyl bridging adjacent Cu(Ⅱ) units to form an infinite chain structure along the c axis. Also, π-π stacking interactions between the adjacent chains expanded the 1-D structures into a 3-D supramolecular structure.     

Synthesis,Crystal Structure and Properties of a Novel Coordination Polymer Based on a Trinuclear Mn（II） Cluster： [Mna（bpta）2（bip）2]n

The coordination polymer, [Mn3（bpta）2（bip）2], （H3bpta = biphenyl-3,3＇,5-tricar- boxylic acid, bip = 2,6-bis（imidazole-1-yl）pyridine）, has been synthesized under hydrothermal con- ditions and characterized by elemental analysis, FT-IR, XRD, TGA and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 14.919（3）, b = 9.780（2）, c = 20.352（7） A, V = 2344.4（10） A3, Z= 2, C52H32Mn3N10012, Mr = 1153.70, Dc = 1.634 g/cm3, p（MoKa） = 0.876 mm-1, F（000） = 1170, the finalR = 0.0605 and wR = 0.1177. The complex forms a 2D layer with trinuclear Mn（II） units and further assembles into a 3D supramolecular network structure through C-H..＇O hydrogen bonding and C-H...π interactions. Moreover, the negative J value indicates the presence of antiferromagnetic coupling between the Mn（II） ions within a trinuclear unit.     

Synthesis and Crystal Structure of a Novel Ca(Ⅱ) Coordination Polymer Containing Dipyridine Dicarboxylic Ligand

The novel alkaline metal complex Ca(BPDCH)2(1, BPDCH2 = 2,2'-bipyridine-5,5'-dicarboxylic acid) has been synthesized by the hydrothermal reaction of Ca(NO3)2·4H2O with 2,2'-bipyridine-5,5'-dicarboxylic acid. The molecular and crystal structures of complex 1 have firstly been characterized by FTIR, elemental analysis, and X-ray single-crystal diffraction. The 3D MOF structure of complex 1 was interpreted by the versatile binding modes-the intermolecular hydrogen bonds and π-π stacking interactions of 2,2'-bipyridine-5,5'-dicarboxylic acid ligand. The analysis results show complex 1 belongs to a coordination polymer with 3D MOF structure. The results of thermogravimetric analysis and solubility demonstrate complex 1 is a thermostable compound and does not dissolve in water and traditional organic solvents.     

Synthesis and Crystal Structures of Two Di-Cu(Ⅱ) Complexes Based on an Asymmetric Dinucleating Ligand

Two new dicopper(II) complexes [Cu2L(OAc)2](ClO4)·H2O(1) and [Cu2L(BPP)2]-(ClO4)(2) using an asymmetric dinucleating ligand HL and auxiliary ligands such as acetate(OAc) and bisphenyl phosphate(BPP) have been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 crystallizes as blue single crystals that belong to the triclinic crystal system and P1 space group, while complex 2 crystallizes in a monoclinic P21/c space group. Single-crystal X-ray diffraction analysis reveals that the two copper ions in complexes 1 and 2 reside within the adjacent ligand compartments and are bridged by the endogenous phenoxo-O from ligand L and the introduction of two desired exogenous carboxylates or phosphates in the bidentate μ-1,3-bridged mode. The coordination geometries of Cu(1) and Cu(2) are both distorted square pyramids.     

A Novel 3D Cu(Ⅱ) Coordination Polymer Containing Mixed Ligands: Synthesis,Crystal Structure and Properties

A novel compound, {[Cu2(nbdc)2(4,4'-bpy)2(H2O)2]·2H2O}n(H2nbdc = 4-nitrobenzene-1,2-dicarboxylic acid, 4,4'-bpy = 4,4'-bipyridine), was hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis(TGA), and single-crystal X-ray diffraction. The complex is of orthorhombic system, space group Pbcn with a = 32.222(7), b = 7.8503(16), c = 28.389(6), V = 7181(3)3, Dc = 1.720 g/cm3, Mr = 929.74, Z = 8, F(000) = 3792, μ = 1.273 mm-1, the final R = 0.0591 and wR = 0.1378 for 4548 observed reflections with I 2σ(I). The compound exhibits a 3D self-penetrating framework with bcu net topology, in which the(46·48)-networks are joined by the H2nbdc and 4,4'-bpy linkers.     

Urothermal Synthesis and Crystal Structure of a Zn（Ⅱ） Coordination Polymer with a 3-D Supramolecular Structure

A new metal-organic coordination polymer [Zn(hfipbb)(e-urea)]n(1,H2hfipbb = 4,4'-(hexafluoroisopropylidene)bis(benzoic acid),e-urea = ethylene urea) has been urothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction.The title complex crystallizes in monoclinic,space group P21/c with a = 13.302(4),b = 10.981(3),c = 13.804(4) ,β = 93.587(5)°,V = 2012.3(10) 3,C20H14N2O5F6Zn,Mr = 541.72,Z = 4,Dc = 0.447 g/cm3, = 0.328 mm-1,F(000) = 272,R = 0.0340 and wR = 0.1107 for 4528 observed reflections(I >2σ(I)).In the structure of compound 1,two Zn(Ⅱ) ions are bridged by two carboxylate groups from two hfipbb ligands to form a dinuclear unit,and each dinuclear Zn(Ⅱ) unit is linked with its two adjacent dinuclear units through four hfipbb ligands into an infinite one-dimensional double-chain.The interesting structural feature of compound 1 is that the one-D double-chains are self-interconnected into a three-D supramolecular structure through hydrogen bonds between the coordinated e-urea molecules and carboxylate oxygen atoms(N1 and O2,N2 and O4).     

A Zinc(Ⅱ) Coordination Framework Based on Terpyridine and 5-Nitroisophthalic Acid Mixed Ligands: Synthesis,Crystal Structure and Fluorescence Property

A new coordination framework, {[Zn(L1)(5-nipc)]·H2O}n(1, L1 = 4ˊ-(4-pyridyl)-4,2ˊ:6ˊ,4ˊˊ-terpyridine, 5-nipc = 5-nitroisophthalic acid), has been prepared under hydrothermal conditions, and determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR and powder X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a = 29.983(9), b = 13.709(3), c = 14.391(3)A, β = 114.93(4)°, V = 5364(2) A3, Dc = 1.493 g/cm3, C28H19N5O7 Zn, Mr = 602.85, F(000) = 2464, μ(Mo Kα) = 0.972 mm-1, Z = 8, R = 0.0935 and w R = 0.1509 for 4724 observed reflections(I 2σ(I)). The structure of 1 exhibits a three-dimensional(3D) network with a layer-pillar structure. The fluorescence property of 1 is also investigated.     

Synthesis and Crystal Structure of a New Pr(Ⅲ)–K(Ⅰ) Heterometallic Oxalate Coordination Polymer

A new 3D heterometallic coordination polymer, namely [K2Pr2(C2O4)4·H2O]n(1), has been successfully synthesized under hydrothermal conditions. X-ray single-crystal diffraction determination reveals that 1 crystallizes in monoclinic system, space group P21/n with a = 12.060(4), b = 8.493(3), c = 15.776(5)(A), β = 93.235(3)°, V = 1613.4(9) 3, Z = 4, Mr = 730.12, Dc = 3.006 Mg/m3, μ = 6.581 mm-1, F(000) = 1368, the final R = 0.0283 and w R = 0.0866 for 2939 observed reflections with I 2σ(I). Complex 1 features an unusual 3D heterometallic coordination framework, in which oxalates exhibit three different coordination behaviours. Moreover, powder X-ray diffraction and thermal properties for 1 have also been investigated.     

Hydrothermal Synthesis and Crystal Structure of a Znic(Ⅱ) Coordination Polymer Assembled by 4-Sulfophthalate and 4,4'-Bipyridine

A new organometallic coordinate polymer {[Zn2(4-sphth)2(4,4'-bpy)4(H2O)4][Zn(4,4'-bpy)2(H2O)4]}n·n[(4,4'-bpy)(H2O)4](4-sphth=4-sulfophthalic acid,4,4'-bpy = 4,4'-bipyridine) 1 has been hydrothermally synthesized and characterized by elemental analysis,IR,fluorescence spectrum and single-crystal X-ray diffraction.The complex crystallizes in monoclinic,space group C2/c with a=18.8659(13),b=23.0861(13),c=22.5449(14),β=107.4120(10)o,V=9369.3(10)3,Mr=1981.86,Dc=1.405 g/cm3,μ(MoKα)=0.891 mm-1,F(000)=4100,Z=4,the final R=0.0644 and wR=0.1615 for 5984 observed reflections(I 2σ(I)).Furthermore,compound 1 shows blue photoluminescent property at room temperature.     

Urothermal Synthesis,Crystal Structure,and Luminescent Property of a New Zn（II） Coordination Polymer Constructed from Terephalic Acid and 5-Methyl-1H-tetrazole Ligands

A new luminescent Zn（II） compound, [Zn（pbdc）0.5（mtz）（DMPU）]n （1,H2pbdc = terephthalic acid, Hmtz = 5-methyl-1H-tetrazole, DMPU = N,N＇-dimethylpropyleneurea）, has been urothermally synthesized and characterized by elemental analysis, IR, X-ray powder diffraction （PXRD） and single-crystal X-ray diffraction. The title compound crystallizes in orthorhombic Pbca space group with α = 17.2649（5）, b = 10.4680（3）, c = 17.4457（7） ？, V = 3152.94（18） ？3, C12H17N6O3Zn, Mr = 358.71, Z = 8, Dc = 1.511 g/cm3, F（000） = 1480, μ = 1.579 mm-1, the final R = 0.0379 and wR = 0.0971 for 2785 observed reflections （I 〉 2σ（I））. Single-crystal X-ray structural analysis reveals that compound 1 features a 2D undulated layer with a 3-connected hcb topology. Moreover, the luminescent properties of 1 have also been investigated in the solid-state at room temperature.     

Synthesis and Crystal Structure of a Novel Cobalt（Ⅱ） Coordination Polymer with 1,2,4,5-Benzenetetracarboxylate

A novel cobalt（II） coordination polymer,[Co（BTEC）1/2]n 1,has been synthesized with Co（NO3）2·6H2O and 1,2,4,5-benzenetetracarboxylic acid （H4BTEC） by the hydrothermal method,and characterized by elemental analysis,IR and single-crystal X-ray diffraction. Crystallographic data for 1： C5HO4Co,Mr = 183.99,monoclinic,space group C2/c,a = 16.619（6）,b = 7.416（3）,c = 8.040（3）A,β = 90.612（4）°,V = 990.8（6） A^3,Z = 8,Dc = 2.467 g/cm^3,μ = 3.390 mm^-1,F（000） = 720,R = 0.0307 and wR = 0.0847 for 912 observed reflections （I 〉 2σ（I））. X-ray crystal structural analysis revealed that each Co（II） adopts a tetrahedral coordination mode to link four separate BTEC ligands via uniform monodentate carboxylate groups and each BTEC ligand possesses an 8-connected geometry to connect eight Co（II） ions. Complex 1 exhibits a rare （4,8）-connected net with （45.6）2（410.614.84） topology.     

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Zinc（II） Complex with 2,2′-Diphenic Acid and 2,2′-Bipyridine Ligands

A new dinuclear complex [Zn(dpa)(bipy)(H2O)]2 (dpa = 2,2'-diphenic acid, bipy = 2,2'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 10.960(2), b = 9.4841(18), c = 20.599(4), β = 104.452(3)o, V = 2073.4(7)3, C48H36N4O10Zn2, Mr = 959.55, Dc = 1.537 g/cm3, μ(MoKα) = 1.225 mm-1, F(000) = 984, Z = 2, the final R = 0.0364 and wR = 0.0843 for 2788 observed reflections (I > 2σ(I)). In the crystal structure, the zinc atom is five-coordinated with two carboxylate oxygen atoms from different dpas, one coordinated water molecule and two nitrogen atoms from bipy ligands, showing a slightly distorted triangular bipyramidal geometry. Furthermore, it exhibits a zero-dimensional network structure with a sixteen-membered ring and shows yellow photoluminescent property at room temperature.     

Synthesis,Crystal Structure and Fluorescent Properties of a 4-Fold Interpenetrating Zn(Ⅱ) Polymer

A new coordination polymer [Zn(isop)(bps)]n 1(H2isop=benzene-1,3-dicer-boxylic acid,bps=4,4'-dipyridyl sulfide) has been prepared and structurally characterized by X-ray diffraction method.It crystallizes in monoclinic,space group P21/n with a=12.1936(11),b=10.7720(9),c=13.0685(11),V=1709.0(3)3,C18H12N2O4SZn,Mr=417.76,Z=4,Dc=1.624g/cm3,S=1.046,F(000)=848,the final R=0.0305 and wR=0.0858 for 3085 independent reflections with Rint=0.0147.Single-crystal X-ray diffraction analyses reveal that 1 is a 4-fold interpenetrating diamondoid network.The zinc(Ⅱ) atom is coordinated by two nitrogen atoms of two bps and two carboxylate oxygen atoms of isop ligands,resulting in a tetrahedral geometry.