Hydrothermal Synthesis and Crystal Structure of a Cadmium(Ⅱ) Polymer with One-dimensional Chain Structure: [Cd(bpy)(BDC)]n·nbpy

A metal-organic coordination polymer [Cd(bpy)(BDC)]n·nbpy (bpy = 2,2'-bipyri- dine, H2BDC = terephthalic acid) has been hydrothermally synthesized and structurally characteri- zed by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group C2/c with a = 15.723(5), b = 21.695(5), c = 7.576(5)(A), β = 116.171(7)o, V = 2319.3(18)(A)3, C28H20CdN4O4, Mr = 588.88, Dc = 1.686 g/cm3, μ(MoKα) = 0.987 mm(1, F(000) = 1184, Z = 4, the final R = 0.0464 and wR = 0.0831 for 1882 observed reflections (Ⅰ ＞ 2σI)). It exhibits a three-dimensional network with channels constructed from one-dimensional coordination chains via C-H…O hydrogen bonds and significant aromatic π-π stacking interactions.     

Hydrothermal Synthesis and Crystal Structure of a Cadmium(II) Polymer with One-dimensional Chain Structure: [Cd(bpy)(BDC)]_n·nbpy

A metal-organic coordination polymer [Cd(bpy)(BDC)]n·nbpy (bpy = 2,2-bipyri- dine, H2BDC = terephthalic acid) has been hydrothermally synthesized and structurally characteri- zed by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group C2/c with a = 15.723(5), b = 21.695(5), c = 7.576(5) , β = 116.171(7)o, V = 2319.3(18) 3, C28H20CdN4O4, Mr = 588.88, Dc = 1.686 g/cm3, μ(MoKα) = 0.987 mm-1, F(000) = 1184, Z = 4, the final R = 0.0464 and wR = 0.0831 for 1882 observed reflections (I > 2σ(I)). It exhibits a three-dimensional network with channels constructed from one-dimensional coordination chains via C–H···O hydrogen bonds and significant aromatic π-π stacking interactions.     

Hydrothermal Synthesis and Crystal Structure of a Cobalt(Ⅱ) Polymer with One-dimensional Chain Structure: [ Co(phen) (BDC)(H2O)]n·0.5nH2BDC

A metal-organic coordination polymer [Co(phen)(BDC)(H2O)]n·0.5nH2BDC(H2BDC = terephthalic acid, phen = 1,10-phenanthroline) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in triclinic, space group P1- with a = 9.771(3), b =10.739(3), c= 11.249(4) (A), α = 75.946(3), β = 65.306(3), γ = 86.073(4)°, V = 1039.6(6)(A)3, C24H17CoN2O7, Mr=504.33, Dc = 1.611 g/cm3, μ(MoKa) = 0.878 mm-1, F(000) = 516, Z = 2, the final R = 0.0547 and wR = 0.1138 for 2916 observed reflections (I＞ 2σ(Ⅰ)). It exhibits a one-dimensional zigzag chain-like structure.     

Synthesis and Crystal Structure of a Novel 2D Cadmium(II) Complex Constructed from N-(3-Carboxyphenyl)-4,4ˊ-bipyridinium and Benzene-1,4-dicarboxylic Acid

A novel redox-active bipyridinium ligand N-(3-carboxyphenyl)-4,4ˊ-bipyridinium chloride (HCPBPyCl) and its coordination polymer {[Cd2(CPBPy)2(BDC)(H2O)2Cl2]·6H2O}n 1 (H2BDC = benzene-1,4-dicarboxylic acid) were synthesized and characterized. Crystallographic data for 1: C42H44Cd2Cl2N4O16, Mr = 1156.51, monoclinic, space group C2/c, a = 21.046(3), b = 11.0036(15), c = 20.012(3) , β = 98.694(8)°, Z = 4, V = 4581.1(11) 3, Dc = 1.677 g/cm3, F(000) = 2280 and μ = 1.120 mm-1. Complex 1 possesses a thick and undulated two-dimensional layer with (6,3) topology, which interpenetrates with two others (above and below) to extend into a three-di-mensional supramolecular framework.     

Hydrothermal Synthesis and Crystal Structure of a Cobalt(Ⅱ) Polymer with One-dimensional Chain Structure: [Co(phen)(BDC)(H_2O)]_n·0.5nH_2BDC

A metal-organic coordination polymer [Co(phen)(BDC)(H2O)]n·0.5nH2BDC (H2BDC = terephthalic acid, phen = 1,10-phenanthroline) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in triclinic, space group P1 with a = 9.771(3), b =10.739(3), c = 11.249(4) , α = 75.946(3), β = 65.306(3), γ = 86.073(4)o, V = 1039.6(6) 3, C24H17CoN2O7, Mr = 504.33, Dc = 1.611 g/cm3, μ(MoKα) = 0.878 mm-1, F(000) = 516, Z = 2, the final R = 0.0547 and wR = 0.1138 for 2916 observed reflections (I > 2σ(I)). It exhibits a one-dimensional zigzag chain-like structure.     

Crystal Structure of a Threedimensional Coordination Polymer {[Ca3(μ5-OOCCH2OCH2COO)3(H2O)4]·4H2O}n

A novel three-dimensional coordination polymer, {[Ca3(μ5-OOCCH2OCH2COO)3(H2O)4]·4H2O}n, has been synthesized with oxydiacetate as bridge ligand and structurally determined by X-ray crystallography. The crystal belongs to monoclinic, space group C2/c with a = 17.805(2), b = 9.3923(12), c = 17.255(2)(A), β = 107.838(5)°, V = 2746.8(6) (A)3, Mr = 660.58, C12H28Ca3O23, Dc = 1.597 g/cm3, μ = 0.695 mm-1, Z = 4, F(000) = 1376, GOOF = 1.027, R = 0.0303 and wR = 0.0660. In the complex there are two coordination modes for Ca(Ⅱ) ions, one coordinated by three μ5-OOCCH2OCH2COO2- bridge ligands together with two H2O molecules, and the other by five μ5-OOCCH2OCH2COO2- bridge ligands. In both coordination modes each Ca(Ⅱ) ion assumes a distorted dipentapyramidal CaO7 geometry; whereas each oxydiacetate is coordinated with five Ca(Ⅱ) ions and acts as a pentdentates bridge ligand.     

Hydrothermal Synthesis and Crystal Structure of a Cadmium（Ⅱ） Polymer with One-dimensional Chain Structure： [Cd（MDPPz）（BDC）（H2O）]n

A metal-organic coordination compound formulated as [Cd(MDPPz)(BDC)(H2O)]n 1 (MDPPz=11-methyldipyrido[3,2-a:2',3'-c]phenazine,BDC=1,4-benzenedicarboxylate) has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,fluorescence spectrum and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system,space group C2/c,with a=30.673(8),b=9.623(3),c=20.784(6) ,β=98.646(3)o,V=6065(3)3,C27H17CdN4O5,Mr=589.85,Dc=1.292 g/cm3,μ(MoKα)=0.757 mm-1,F(000)=2360,Z=8,the final R=0.0381 and wR=0.0855 for 4191 observed reflections (I>2σ(I)). 1 exhibits blue fluorescence property at room temperature.     

Synthesis, Structure and Luminescent Properties of a New Terbium（Ⅲ） Complex with 5-Bromoisophthalic Acid

The self-assembly of 5-bromoisophthalic acid (H2BIPA) with Tb(NO3)3·6H2O under hydrothermal conditions gives rise to a 3D coordination polymer, [Tb2(BIPA)3(CH3CH2OH)]n (1), which was characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal is of monoclinic system, space group P21/c with a = 19.2591(17), b = 8.2537(7), c = 18.5663(17), β = 104.4720(10)°, V = 2857.6(4)3, C26H15Br3O13Tb2, Mr = 1092.95, Dc = 2.540 g/cm3, F(000) = 2040, μ = 9.173 mm-1 and Z = 4. The final R = 0.0324 and wR = 0.0767 for 5299 observed reflections (I > 2σ(I)). Complex 1 displays an unusual three-dimensional (4,6)-connected network with (48.66.8)2(44.62)2(42.84) topology, which is different from [Tb(HBDC)(BDC)(H2O)4]·3.3H2O (BDC = isophthalate) because the -Br substituent of isophthalate results in different electronic effect and steric hindrance to change the coordination modes of carboxylate groups in the assembly process. Moreover, luminescent properties of 1 have also been investigated in the solid state.     

Crystal Structure of a Three-dimensional Coordination Polymer {[Ca_3(μ_5-OOCCH_2OCH_2COO)_3(H_2O)_4]·4H_2O}_n

A novel three-dimensional coordination polymer, {[Ca3(μ5-OOCCH2OCH2COO)3(H2O)4]- 4H2O}n, has been synthesized with oxydiacetate as bridge ligand and structurally determined by X-ray crystallography. The crystal belongs to monoclinic, space group C2/c with a = 17.805(2), b = 9.3923(12), c = 17.255(2) A, β = 107.838(5)°, V = 2746.8(6) A3, Mr = 660.58, C12H28Ca3O23, Dc = 1.597 g/cm3, μ = 0.695 mm-1, Z = 4, F(000) = 1376, GOOF = 1.027, R = 0.0303 and wR = 0.0660. In the complex there are two coordination modes for Ca(II) ions, one coordinated by three μ5-OOCCH2OCH2COO2- bridge ligands together with two H2O molecules, and the other by five μ-5-OOCCH2OCH2COO2 bridge ligands. In both coordination modes each Ca(II) ion assumes a distorted dipentapyramidal CaO7 geometry; whereas each oxydiacetate is coordinated with five Ca(II) ions and acts as a pentdentates bridge ligand.     

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.     

Synthesis and Crystal Structure of [{Cd(hmbdc)(H2O)3}·2H2O]n

A novel coordination polymer [{Cd(hmbdc)(H2O)3}·2H2O]n (hmbdc=5-hydroxy- isophthalic acid) has been synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c, with a=9.599(3), b=18.699(5), c=7.557(2) (A), β= 108.198(4)°, V=1288.6(6) (A)3, Z=4, Mr=382.60, Dc=1.972 g/cm3, F(000)=760, μ=1.740, the final R=0.0555 and wR=0.0995 for 1732 observed reflections with Ⅰ ＞ 2σ(Ⅰ). The structural analysis shows that the intermolecular hydrogen bonds and π-π interactions result in a three-dimensional supramolecular framework.     

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.     

Hydrothermal Synthesis, Structure and Photoluminescence of a 2D Lead(Ⅱ) Coordination Polymer with (4,3 6) Topology Based on Pb and 1,2,3,4-Butanetetracarboxylate Nodes

A lead(Ⅱ) coordination polymer, {[Pb2(butca)(H2O)2](H2O)2}n (1), has been synthesized by the hydrothermal reaction of Pb(OH)2 and 1, 2, 3, 4-butanetetracarboxylic acid (H4butca) at 160 ℃. Single-crystal X-ray analyses reveal that it crystallizes in monoclinic, space group P21/c with a = 7.616(5), b = 7.584(4), c = 12.314(7) (A), β = 105.595(12)°, V = 685.0(7) (A)3, Z = 4,C8H14O12Pb2, Mr= 716.57, Dc=3.474 g/cm3,μ = 24.610 mm-1, F(000) = 644, the final R = 0.0381 and wR = 0.1176 for 1465 observed reflections with Ⅰ＞ 2σ(Ⅰ). The complex presents a 2D-layered structure featuring two different types of rings, and has a (4,3 6) topology based on Pb and butca 4- nodes. In solid state, complex 1 shows photoluminescence with the maximum emission intensity at 468 nm under 286 nm excitation.     

Synthesis,Crystal Structure and Properties of the Cobalt(Ⅱ) Complex of Methyl-5-norbornene-2,3-dicarboxylic Acid

A new cobalt complex Co(C10H8N2)(H2O)3[C9H11O2(COO)] with methy-5-norbornene-2,3-dicarboxylic anhydride acid(MNA) and 2,2'-bipyridine as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in monoclinic, space group P21/c with a = 13.0430(13), b = 21.014(2), c = 7.5151(7) ?, β = 102.319(2)o, V = 2012.4(3) ?3, Dc = 1.529 g/cm3, Z = 4, F(000) = 964, GOOF = 1.051, the final R = 0.0457 and wR = 0.0974. The crystal structure shows that the cobalt ion is coordinated with four oxygen atoms from one MNA molecule and three water molecules together with two nitrogen atoms from the 2,2'-bipyridine molecule, forming a distorted octahedral coordination geometry. The thermal stability and electrochemical properties have studied in this paper.     

Synthesis and Crystal Structure of [Zn(FcCOO)2(2,2′-bipy)(H2O)]2·H2O

A novel complex [Zn(FcCOO)2(2,2′-bipy)(H2O)]2·H2O (Fc = (η5-C5H5)Fe(η5-C5H4), 2,2′-bipy = 2,2′-bipyridine) has been synthesized and characterized by elemental analysis, IR and X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 6.8187(4), b = 21.7155(13), c = 19.7411(12) (A), α = 90, β = 97.7420(10), γ = 90°, C64H58Fe4Zn2N4O11, Mr = 1413.28, V = 2896.4(3) (A)3, Dc = 1.620 g/cm3, Z = 2, F(000) = 1444, μ(MoKα) = 1.857 mm-1, R = 0.0523 and wR = 0.0982 for 3219 observed reflections (I ＞ 2σ(I)). Structural analysis shows that the zinc atom is coordinated with three oxygen atoms from two ferrocenemonocarboxylates and one water molecule together with two nitrogen atoms from 2,2′-bipyridine, giving a distorted square-pyramidal coordination geometry. The complex molecules are linked to form an infinite one-dimensional chain by both intermolecular hydrogen bonds and π-π stacking interactions of the bipyridine rings.     

hree Inorganic-organic Composite Polyoxotungstates:Syntheses, Characterization and Structures of [Cu(2,2'-bpy)2]5[α-PW11.5Cu0.5O40]·2H2O,[Co(2,2'-bpy)2(N3)2]4H3[α-PW12O40]·3H2O and [Cu(2,2'-bpy)2(4,4'-bpy)]2[α-GeW12O40]·4H2O

Three new inorganic-organic composite polyoxotungstates [Cu(2,2'- bpy)2]5[α- PW11.5Cu0.5O40]·2H2O 1, [Co(2,2'-bp3)2(N3)2]4H3[α-PW12O40]·3H2O 2 and [Cu(2,2'-bpy)2(4,4'- bpy)]2[α-GeW12O40].4H2O 3 (2,2'-bpy = 2,2'-bipyridine, 4,4'-bpy = 4,4'-bipyridine) have been hydrothermally synthesized and structurally characterized. 1 crystallizes in the orthorhombie space group Pna21 with α = 27.847(3), b = 21.597(2), c = 20.1179(19) A, V = 12099(2) A3, Z = 4, GOF= 1.038, R = 0.0427 and wR = 0.1035; 2 belongs to the triclinic space group P1 with a= 12.31150(10), b = 16.1954(4), c = 19.36290(10) A, α = 99.366(11), β=105.168(8),γ = 111.836(8)°, V = 3309.98(9) A3, Z = 1, GOF = 1.024, R = 0.0739 and wR = 0.2216; and 3 crystallizes in the monoclinic space group P21/n with a = 12.858(4), b = 20.943(6), c = 15.598(5) A, β = 102.338(5)°, V = 4103(2) A3, Z = 2, GOF = 1.026, R = 0.0557 and wR = 0.1316. The common structural features of 1～3 are that their molecular structures all consist of a saturated a-Keggin polyoxoanion and several discrete metal-organic moieties. Intriguingly, 2 and 3 are composed of metal-organic coordination moieties with two mixed ligands.     

Synthesis and Crystal Structure of [Zn(FcCOO)2(2,2′-bipy)(H2O)]2·H2O

A novel complex [Zn(FcCOO)2(2,2′-bipy)(H2O)]2·H2O (Fc = (η5-C5H5)Fe(η5-C5H4), 2,2′-bipy = 2,2′-bipyridine) has been synthesized and characterized by elemental analysis, IR and X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 6.8187(4), b = 21.7155(13), c = 19.7411(12) (A), α = 90, β = 97.7420(10), γ = 90°, C64H58Fe4Zn2N4O11, Mr = 1413.28, V = 2896.4(3) (A)3, Dc = 1.620 g/cm3, Z = 2, F(000) = 1444, μ(MoKα) = 1.857 mm-1, R = 0.0523 and wR = 0.0982 for 3219 observed reflections (I ＞ 2σ(I)). Structural analysis shows that the zinc atom is coordinated with three oxygen atoms from two ferrocenemonocarboxylates and one water molecule together with two nitrogen atoms from 2,2′-bipyridine, giving a distorted square-pyramidal coordination geometry. The complex molecules are linked to form an infinite one-dimensional chain by both intermolecular hydrogen bonds and π-π stacking interactions of the bipyridine rings.     

Synthesis and Crystal Structure of a One-dimensional Silver(Ⅰ) Coordination Polymer with 4,4'-Bipyridine

The title compound,{[Ag2(bipy)2(H2O2]·pydc·2H2O}n(bipy=4,4'-bipyridine,pydc=pyridine-3,5-dicarboxylate),has been synthesized by the reaction of Ag2O with pydc and bipy in CH3OH solution.It crystallizes in the monoclinic system,space group C2/c with a=21.419(8),b=7.515(3),c=18.070(7)(A),β=108.273(6)°,Mr=765.27,V=2761.9(17)(A)3,Z=4,Dc=1.840 g/cm3,F(000)=1528,μ=1.478 mm-1,the final R=0.0307 and wR=0.0681.The structure determined demonstrated that the Ag(Ⅰ)is three-coordinated by two nitrogen atoms from bipy and one water molecule,forming a one-dimensional coordination polymer[Ag2(bipy)2(H2O)2]n2n ,which is further linked to generate a two-dimensional layer structure via Ag…Ag attractions.     

Crystal Structure of Catena-poly-[2,2'-bisbenzimidazole Mn(Ⅱ)-μ-Benzene-1,3-dicarboxylato]

The title complex,[(BBI)Mn(BDC)]n 1(BBI = 2,2'-bisbenzimidazole(C14H10N4),BDC=benzene-1,3-dicarboxylate dianion(C8H10O4)),crystallizes in the monoclinic system,space group C2/c,with a=17.822(8),b=16.181(7),c=13.355(6),β=92.112(5)°,V=3848.67(304)3,Z=8,C22H14MnN4O4,Mr=453.31,Dc=1.565 g/cm3,F(000)=1848,μ=0.725 mm-1,S=1.000,the final R=0.0310 and wR=0.0589.1 contains hydrogen bonds and π-π stacking interactions between the neighboring aryl-ring of BBI's,which helps to form a three-dimensional crystal structure.     

Synthesis and Crystal Structure of [Zn(FcCOO)_2(2,2'-bipy)(H_2O)]_2·H_2O

A novel complex [Zn(FcCOO)2(2,2'-bipy)(H2O)]2·H2O (Fc = (η5-C5H5)Fe(η5-C5H4), 2,2'-bipy = 2,2'-bipyridine) has been synthesized and characterized by elemental analysis, IR and X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 6.8187(4), b = 21.7155(13), c = 19.7411(12) A, α = 90, β = 97.7420(10), γ = 90o, C64H58Fe4Zn2N4O11, Mr = 1413.28, V = 2896.4(3) A3, Dc = 1.620 g/cm3, Z = 2, F(000) = 1444, μ(MoKα) = 1.857 mm-1, R = 0.0523 and wR = 0.0982 for 3219 observed reflections (I > 2σ(I)). Structural analysis shows that the zinc atom is coordinated with three oxygen atoms from two ferrocenemonocarboxylates and one water molecule together with two nitrogen atoms from 2,2'-bipyridine, giving a distorted square-pyramidal coordination geometry. The complex molecules are linked to form an infinite one-dimensional chain by both intermolecular hydrogen bonds and π-π stacking interactions of the bipyridine rings.