Construction of a 2D Cd（II） Coordination Polymer Based on a V-shaped Bidentate Ligand

A two-dimensional（2D）coordination polymer{[Cd（bdc）（dpb）]·H2O}n（1）has been prepared by solvothermal reaction of 1,3-dipyridyl benzene（1,3-dpb）with deprotonated1,4-benzenedicarboxylate（H2bdc）,and was characterized by elemental analysis,IR spectroscopy,and X-ray single-crystal diffraction.It crystallizes in the monoclinic system,space group C2/c with a=15.1839（12）,b=20.7585（17）,c=7.2989（6）,β=117.3450（10）°,V=2043.5（3）3,C24H18N2O5Cd,Mr=526.81,Dc=1.712 g/cm3,F（000）=1056.0,μ=1.110 mm-1and Z=4.The neighboring Cd（II）ions link the bdc2-anions and 1,3-dpb to form an infinite 2D sheet,and such two2D sheets are interlocked with each other to form a 2D→2D sheet.Two groups of interlocked sheets are further linked together by intermolecularπ···πinteraction,giving a 3D supramolecular network.In addition,the fluorescence property of 1 was also studied.     

Construction of a 3D Co(Ⅱ) Framework Based on Two Types of V-shaped Bidentate Ligands

A three-dimensional(3D) coordination polymer {[Co(bdc)(dpb)]·H2O}n(1) was prepared by solvothermal reaction of 1,3-dipyridyl benzene(dpb) with deprotonated 1,3-benzenedicarboxylate(H2bdc), and was characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group C2/c with a = 15.478(6), b = 12.865(5), c = 24.091(10) ?, β = 95.599(5)°, V = 4774(3) ?3, C24H18CoN2O5, Mr = 473.34, Dc = 1.267 g/cm3, F(000) = 1864.0, μ = 0.748 mm-1 and Z = 8. Each Co(II) ion links three bdc2- anions to form an infinitely 1D ladder-shaped chain containing binuclear [(COO)Co]2 cluster, and dpb links adjacent 1D chains to form a 3D pcu framework. In addition, the UV-vis of 1 was also studied.     

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.     

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.     

Two Cadmium（Ⅱ） Coordination Polymers from Flexible Bis（imidazolyl） Ligands

The hydrothermal reaction of 1,4-bis(imidazol-1-yl)butane (bimb) and 1,4-bis(2- methylimidazol-1′-yl)butane (bmib) with CdBr2-4H2O gave rise to two coordination polymers, [Cd(bimb)2Br2]n (1) and [Cd(bmib)Br2]n (2), respectively. Single-crystal X-ray diffraction analysis reveals that 1 and 2 crystallize in the monoclinic space group P21/n and the orthorhombic space group Pccn, respectively. In 1, bimb adopts an anti-anti-anti conformation and bridges adjacent Cd(II) to form a two-dimensional (2D) network containing rhombohedral rings. The 2D layers are arranged in an offset ABCABC sequence to fill large void in the rhombohedral rings. In 2, bmib also exhibits an anti-anti-anti conformation, but it links neighboring Cd(II) into a one-dimensional (1D) chain. Br- in 1 and 2 serves as a monodentate ligand to balance charge.     

Hydrothermal Synthesis and Crystal Structure of One 3D Coordination Polymer of Nickle （II） Achieved from 5-Iodo-isophthalic Acid Ligand

A new coordination polymer [Ni（L）（m-bix）（H2O）]n （1, H2L = 5-iodo-isophthalic acid, m-bix=1,3-bis（imidazol-1-ylmethyl）-benzene） has been synthesized by the hydrothermal method and characterized by IR, elemental analysis, powder XRD and single-crystal X-ray analysis. The crystal is of triclinic, space group Pī with a = 9.1638（3）, b = 10.2319（3）, c = 13.2463（4） ？, α = 80.1710（10）, β = 83.671（2）, γ = 70.3790（10）o,C22H19NiIN4O5, Mr = 605.02, V = 1150.85（6） ？3, Dc = 1.746 g/cm3, F（000） = 600, μ = 2.225 mm-1, S = 1.045 and Z = 2. The final R = 0.0388 and wR = 0.1257 for 5089 observed reflections with I 〉 2σ（I）. In the title complex, the M and P layers are arranged alternately to give a double-layer structure by the symmetry related hydrogen bonds, and these double-layers are further joined together to achieve a 2D supramolecular architecture through I···π interaction involving iodine atoms and imidazole rings. The thermal stability of the title complex was studied by thermal gravimetric （TG） and differential thermal analysis （DTA）.     

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.     

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.     

A Three-dimensional Cd(Ⅱ) Coordination Polymer with Unique 8-Connected LOMFOI Topology Based on Mixed Flexible N/O Ligands

A new metal-organic framework,{[Cd(DPA)(OBA)]·(H2O)}n(1,DPA = 4,4-dipyridylamine,H2OBA = 4,4-oxybisbenzoic acid),has been synthesized and characterized by elemental analysis,IR and single-crystal X-ray diffraction.Single-crystal X-ray analysis shows that it is a 3-D framework.Complex 1 crystallizes in monoclinic,space group C2/c with a = 21.699(7),b = 12.192(4),c = 17.566(5) ,β = 105.254(5)°,V = 4483.43 3,Z = 8,Dc = 1.653 g/cm3,μ = 1.021 mm-1,F(000) = 2240,the final R = 0.0307,wR = 0.0867(I 2σ(I)).Complex 1 exhibits a rare three-dimensional highly 8-connected LOMFOI topology with a point symbol of {424·64}.Thermogravimetric analysis shows that the decomposition temperature of the host framework of the complex is above 400 ℃.     

Synthesis,Crystal Structures and Magnetic Properties of Cobalt（II） and Manganese（II） Coordination Polymers Constructed from 5-（Pyridin-4-yl）isophthalate Ligands

Two coordination polymers, namely {[Co（L）（H2O）]·H2O}n （1） and [Mn（L）（phen）]n （2, H2L = 5-（pyridin-4-yl）isophthalic acid, phen = 1,10-phenanthroline）, have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. 1 belongs to the triclinic system, space group Pī with α = 7.2188（7）, b = 10.0835（8）, c = 10.2069（7） ？, α = 113.713（7）, β = 99.490（7）, γ = 104.516（8）o, V = 628.24（9） ？3, C13H11NCoO6, Mr = 336.16, Z = 2, Dc = 1.777 Mg/m3, μ（MoKα） = 1.395 mm–1, F（000） = 342, S = 1.041, the final R = 0.0381 and wR = 0.0819 for 3744 observed reflections （I 〉 2σ（I）） and R = 0.0448 and wR = 0.0874 for all data. 2 belongs to the monoclinic system, space group P2/c with α = 12.9185（3）, b = 10.4343（2）, c = 31.7650（6） ？, β = 101.282（2）o, V = 4199.08（13） ？3, C50H30N6Mn2O8, Mr = 952.68, Z = 4, Dc = 1.507 Mg/m3, μ（MoKα） = 5.447 mm–1, F（000） = 1944, S = 1.128, the final R = 0.1003 and wR = 0.1052 for 8247 observed reflections （I 〉 2σ（I）） and R = 0.2595 and wR = 0.2625 for all data. Single-crystal X-ray diffraction studies show that compound 1 features a 2D sheet structure based on a dicobalt（II） subunit, which is further extended into a 3D metal-organic supramolecular framework by O–H… hydrogen bond. Compound 2 also possesses a 2D sheet, which is held together into a 3D supramolecular architecture via C–H… hydrogen bond and π-π stacking interactions. Magnetic studies for compound 2 show antiferromagnetic coupling between the adjacent metal centers, with J = –11.8 cm–1 and g = 2.12 for 2.     

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.     

Construction of One New 3D Zinc-organic Framework Based on D-（＋）-camphoric Acid and Bis（4-pyridylmethyl）piperazine

A new polymer [Zn2（cam）2（bpmp）]n 1 （H2cam = D-（＋）-camphoric acid, bpmp = bis（4-pyridylmethyl）piperazine） was synthesized under hydrothermal conditions. The compound crystallizes in the monoclinic system, space group P21/n with a = 12.305（9）, b = 12.945（9）, c = 13.619（10） A, β = 116.833（8）°, V= 1936（2）A3, Z = 4, Mr = 397.76, Dc= 1.365 Mg/m3,μ = 1.292 mm-1, F（000） = 832, the final R = 0.0578 and wR = 0.1678 for 2838 observed reflections with I 〉 2σ（I）. The compound presents a three-dimensional （3D） network extended by homochiral 2D layer and bpmp ligands. From the topology point of view, the structure could be described as a 3D 6-connected mab net with （44.610.8） topology. In addition, infrared spectroscopy, elemental analyses, thermogravimetric analysis and powder X-ray diffraction properties of 1 are also investigated.     

Solvothermal Synthesis and Crystal structure of a Two-dimensional Cd（Ⅱ） Complex Based on a Flexible Carboxylate Ligand

A two-dimensional Cd(II) coordination polymer, [Cd(dtb)]n (dtb=5,5-dithiobis(2- nitrobenzoic acid), has been solvothermally synthesized and characterized by elemental analysis, IR, TG analysis and single-crystal X-ray diffraction analysis. The complex crystallizes in the monoclinic P21/c space group, with a=10.7147(10), b=7.4518(7), c=22.053(2), β=95.477(2)o, V=1752.7(3)3, Z=4, Mr=524.74, Dc=1.989 g/cm3 and F(000)=1032. The final R=0.0453 and wR=0.1201 for 2950 observed reflections with I>2σ(I). In the complex, the Cd(II) ion is coordinated with six oxygen atoms from four different carboxylate groups of dtb ligands and one lattice water molecule. The adjacent Cd centers are interconnected by the flexible carboxylate ligand to form a two-dimensional (2D) structure.     

Hydrothermal Synthesis and Crystal Structure of a Three-dimensional Cadmium（II） Complex

A metal-organic coordination polymer [Cd2(PDC)2(bix)(H2O)2]n ·nH2O(H2PDC=2,4-pyridinedicarboxylic acid, bix=1,4-bis(imidazol-1-ylmethyl)-benzene) 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Brown crystals crystallize in the orthorhombic system, space group P2 12 12 1 with a=11.741(3), b=14.190(4), c=18.963(5) , V=3159.4(14) 3 , C28H26Cd2N6O11, Mr=847.35, Dc=1.781 g/cm3 , F(000)=1680, Z=4, μ(MoKα)=1.415 mm 1 , the final R=0.0381 and wR=0.0882 for 5472 observed reflections (I >2σ(I)). The structure of 1 exhibits a threedimensional network structure.     

A New 4-Connected Ni~Ⅱ Coordination Polymer with a Novel 3D 2-Fold Interpenetrated Framework

A coordination polymer [Ni(pbc)2(H2O)]n(Hpbc = 3-pyrid-4-ylbenzoic acid) has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction,IR and elemental analysis.The crystal is of monoclinic,space group C2/c with a=19.624(5),b=12.029(5),c=19.452(5),β=104.45(5)°,C24H18NiN2O5,Mr=473.11,V=4447(2)3,Dc=1.413 g/cm3,F(000)=1952,μ = 0.91 cm-1,Z = 8,the final R=0.0424 and wR=0.0871 for 3757 reflections with I2σ(I).X-ray diffraction analysis reveals that the pbc-ligands act as diconnectors to link two Ni(Ⅱ) centers and adopt two coordination modes of μ2-N,O and μ2-N,O,O to form infinite wavy nickel-carboxylate chains along the bc plane.The topological analysis of compound [Ni(pbc)2(H2O)]n reveals that it is a typical CdS framework.     

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）.     

Controlled Self-assembly of Two Coordination Polymers via subtly Varying Bis（2-methyl imidazole） Ligands： from 3-Connected （6,3） Net to 4-Connected sql Net①

Two coordination polymers constructed from 3,4-thiophenedicarboxylic acid and bis(2-methyl imidazole) ligands, namely, {[Cd2(tdc)2(bip)2]·7H2O}n(1) and [Cd(tdc)(bib)]n(2)(H2tdc = 3,4-thiophenedicarboxylic acid, bip = 1,3-bis-(imidazol-2-methyl)propane and bib = 1,4-bis(imidazol-2-methyl)butane), have been synthesized and structurally characterized by single-crystal X-ray diffraction. Structural analyses reveal that 1 exhibits a two-dimensional(2D) layered network with 3-connected(6,3) topology, which is further connected into a threedimensional(3D) supramolecular structure by intermolecular hydrogen bonds. However, 2 features a 2D network which can be rationalized as a 4-connected sql net. The results indicate the subtle difference of auxiliary bis(imidazol-2-methyl) ligands may lead to diverse architectures. Moreover, they exhibit luminescence emission in the solid state at room temperature.     

A Novel 3D Heterobimetallic Cyano-bridged Coor- dination Polymer {（NH4）2[Cd（H20）Fe（CN）6]}n： Synthesis and Crystal Structure①

A novel heterobimetaUic coordination polymer, {（NH4）2[Cd（H20）Fe（CN）6]}n 1, has been synthesized by using the slow diffusion method and structurally characterized by elemental analysis, 1R spectroscopy and single-crystal X-ray diffraction. The crystal crystallizes in the monoclinic system, space group P21/n, a = 7.4202（16）, b = 14.939（3）, c = 10.868（2） A and ,8 = 91.660（3）°. For 1, five CN groups of Fe（CN）6]4- are involved in bridging. The polymer displays a 3D open microporous framework with 5-connected uninodal （46.64） topology.     

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).     

Syntheses and Crystal Structures of Three Cadmium（II） Coordination Complexes Based on Flexible 1,2-Bis（imidazol-1~ˊ-yl）ethane

Three Cd（II） coordination complexes,{[Cd（bime）3]（NO3）2·（H2O）3}n（1）,[Cd（bime）Br2]n（2） and [（H2bime）（CdBr4）（H2O）]n（3）（bime = 1,2-bis（imidazol-1-yl）ethane）,have been prepared and characterized.Single-crystal X-ray diffraction analysis reveals that 1~3 crystallize in the trigonal space group P-3,monoclinic space group C2/c and triclinic space group P1,respectively.In 1,bime bridges six-coordinated Cd（II） to generate a two-fold interpenetrating 3D coordination polymer,in which NO3- is not involved in coordination,but serves as a void filler to balance the charge of the 3D framework.The six NO3- and six uncoordinated water molecules form an unprecedented 24-membered macrocycle through hydrogen bonding interaction.In 2,bime in an anti-conformation links the CdBr2 units into a zigzag chain.In 3,bime does not take part in coordination,but is protonated to act as a counter cation of [CdBr4 ]2-.The hydrogen bonds between H2bime and [CdBr4]2- result in the formation of a supramolecular chain.