CRYSTAL STRUCTURE OF A TRINUCLEAR COBALT COMPLEX Co_3(bdt)_3(PBu_3~n)_3 · ~2CH_2C1 (bdt = S_2C_6H_4~2- ) WITH MIXED o-BEN-ZENEDITHIOLATE AND TRIBUTYLPHOSPHINE LIGANDS

Co3(S2C6H4)3{P(C4H9)3}3 ·2CH2Cl2, Mr = 1373. 45, mono-clinic, space group P21/c, a = 16. 110(5), b=36.313(10), c=13. 502(5) A , β= 105. 69(4)% V=7604. 4 A3, Z = 4, Dc = 1. 20 g. cm-3, μ=10. 03 cm-1, and F (000) = 2990. R(Rw) is 0. 086(0. 091) for 4559 observed unique reflections. The three cobalt atoms in the complex form an isosceles triangle with an average Co -Co bond distance of 2. 504(5) A. The average values of Co - S and Co - P bond distances are 2. 271(7) A , and 2. 198(8) A , respectively.

Hydrothermal Synthesis,Crystal Structure and Magnetic Properties of a Novel Cobalt Complex Based on Biphenyl-3,3',4,4'-tetracarboxylate

A novel cobalt complex,[Co2（bptc）（bix）1.5]（1,H4bptc=3,3＇,4,4＇-biphenyltetra-carboxylic acid,bix = 1,4-bis（imidazol-1-ylmethyl）benzene）,has been hydrothermally prepared and characterized by IR spectroscopy,elemental analysis and single-crystal X-ray diffraction.The crystal is of triclinic system,space group P1 with a=10.770（7）,b=12.245（8）,c=13.514（9）,α=102.829（8）,β=107.734（8）,γ=98.833（9）°,C37H27N6O8Co2,Mr=801.51,V=1607.5（18）3,Dc=1.656g/cm3,F（000）=818,μ=1.100mm-1,Z=2,the final R = 0.0694 and wR = 0.1543 for 3034 observed reflections（I2σ（I））.In the title complex,the two Co（Ⅱ） ions are in different coordination environments with distorted octahedral and trigonal bipyramidal geometries,respectively.The Co atoms are linked together through hexadentate bptc ligands,giving rise to 2D layers which are bridged by the bix ligands into a 3-D supramolecular network.Magnetic susceptibilities of 1 reveal weak antiferromagnetic exchange interactions between the adjacent Co（Ⅱ） ions.

Hydrothermal Synthesis, Crystal Structure, Magnetic Properties and Network Topology of a Novel Binuclear Co(Ⅱ) Coordination Polymer_∞~1[Co_2(4,4'-bpy)_2(L)_4](bpy = Bipyridine, HL = 2-Fluorbenzoic Acid)

One novel binuclear Co（Ⅱ） coordination polymer ∞ [Co2（4,4＇-bpy）2（L）4] （1, bpy = bipyridine, HL = 2-fluorbenzoic acid） has been hydrothermally synthesized and structurally characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complex 1 crystallizes in the monoclinic system, space group P21/c with a = 11.163（2）, b = 21.943（4）, c = 9.6381（19） A, β = 113.92（3）°, V= 2158.2（7） A3, Z= 4, Dc = 1.518 g/cm^3, Mr = 493.31, F（000） =1004, R = 0.0303 and wR = 0.0808 for 3614 observed reflections （I〉 2σ（I））. Complex I exhibits a 3D Schlafli symbol （4.62）（4.66.83） topological framework, and the magnetic characterization shows weak antiferromagnetic coupling exchange between two Co ions.

Synthesis and Crystal Structure of a New Mononuclear Cobalt(Ⅲ) Complex with 2,2′-Dipyridylamine and Glycine as Ligands

A new mononuclear cobalt（Ⅲ） complex [Co（dpa）2（Gly）]（ClO4）2-4H2O was synthesized by the reaction of Co^2＋, glycine （gly） and 2,2＂-dipyridylamine （dpa） in a methanol-water solution, and its structure was characterized by IR, EA, ES-MS and X-ray structure analysis. The compound crystallizes in the monoclinic system, space group P21/n with a = 12.8795（2）, b = 13.2904（2）, c = 19.1104（2）A, β= 109.378（1）°, V = 3085.89（8）A^3, Z = 4, Mr = 746.36, Dc = 1.606 g/cm^3, μ= 0.808 mm^-1, F（000） = 1536, the final R = 0.0543 and wR = 0.1306 for 5393 independent reflections. The magnetic measurement of the compound at room temperature shows that it is diamagnetic and the cobalt ion is in low spin ＋3 oxidation state. ES-MS experiments show that the [Co（dpa）E（Gly）]^2＋ cation is very stable in the methanol solution.

Hydrothermal Syntheses and Crystal Structures of Cobalt(Ⅱ) Complexes Constructed by Dipyrido[3,2-a:2',3'-c]phenazine and Different Carboxylate Ligands

Two new metal-organic complexes,{[Co2（bptc）（DPPZ）2（H2O）2]·H2O}n 1 and {[Co2（ccm）2（DPPZ）2]·2H2O}n 2,were obtained by the hydrothermal reactions of Co（NO3）2·6H2O with chelating ligand dipyrido[3,2-a：2＇,3＇-c]phenazine（DPPZ） and the corresponding carboxylic acid,namely,3,3＇,4,4＇-benzophenonetetracarboxylic acid（H4bptc） or 2-carboxycinnamic acid（H2ccm）,respectively.The complexes were structurally characterized by single-crystal X-ray diffraction,elemental analyses,IR spectra,and thermal gravimetry.1 presents unique chiral chain structures,which are further consolidated into three-dimensional supramolecular frameworks via noncovalent bonds,such as hydrogen bonding and π-π interactions.2 features infinite double-chain structures,which are connected by strong π-π interactions to result in three-dimensional supramolecular architectures.

Synthesis and Crystal Structure of a Cobalt(Ⅱ) Complex with 2-(4'-Chlorine-benzoyl)-benzoic Acid and 1,10-Phenanthroline

A new metal-organic complex Co2（cbba）4（phen）2（μ2-OH2）（H2cbba=2-（4＇-chlorine-benzoyl）benzoic acid,phen=1,10-phenanthroline） 1 has been hydrothermally synthesized and struc-turally characterized by single-crystal X-ray diffraction,elemental analyses,TG and IR spectroscopy.The compound crystallizes in triclinic,space group P1 with a=10.7659（7）,b=17.1856（11）,c=19.2022（13）,α=83.8120（10）,β=84.9930（10）,γ=87.2070（10）°,V=3515.8（4）3,C80H50Cl4Co2N4O13,Mr=1534.90,Dc=1.450 g/cm3,μ（MoKα）=0.693 mm-1,F（000）=1568,Z=2,the final R=0.0490 and wR=0.1092 for 8216 observed reflections（Ⅰ 〉2σ（Ⅰ））.In the crystal structure,the cobalt atom is six-coordinated with three carboxylate oxygen atoms from three different cbba ligands,one oxygen atom from coordinated water molecule and two nitrogen atoms from phen ligand,showing a distorted octahedral geometry.Furthermore,it exhibits a 3D supramolecular network through π-π and hydrogen bonding interactions.

Hydrothermal Synthesis and Crystal Structure of a New One-dimensional Cobalt(Ⅱ) Complex with 2-Pyridinecarboxyic Acid and 4,4′-Bipyridine Ligands

A new metal-organic coordination polymer [Co（2-pya）2（4,4＇-bipy）]2n-[（4,4＇- bipy）0.5· H2O]2n （2-pya = 2-pyridinecarboxylic acid, 4,4＇-bipy = 4,4＇-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in tetragonal, space group I41/a with a = b = 22.719（2）, c = 10.710（2）/k, V = 5527.8（14） A3, C54H46N10Co2O10, Mr= 1112.87, Dc = 1.337 g/cm3,μ（MoKa） = 0.665 mm-1, F（000） = 2296, Z = 4, the final R = 0.0633 and wR = 0.1096 for 1261 observed reflections （I 〉 2σ（I））. It exhibits a one-dimensional chain-like structure constructed by mixed ligands of 2-pyridinedicarboxylic acid and 4,4＇-bipyridine.

Synthesis and Crystal Structure of a Dinuclear Cobalt(II) Complex [Co_2(1H-benzimidazole)_4(1,4-bdoa)_2]

A novel dinuclear complex with an empirical formula [Co2(1H-benzimidazole)4(1, 4-bdoa)2] (1,4-bdoa2– = benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 11.000(2), b = 19.385(4), c = 11.417(2) ?, β = 95.49(3)o, V = 2423.3(8) ?3, Z = 2, Mr = 1074.77, Dc = 1.473 g/cm3, μ = 0.760 mm–1, F(000) = 1108, the final R = 0.0645 and wR = 0.0714 for 3273 observed reflections (I > 2σ(I)). Two octahedrally coordinated Co(II) atoms are bridged by two 1,4-bdoa2– groups, generating a macrocyclic ring complex. The Co…Co separa- tion is 7.677(3) ?. An extended 3-D supramolecular network is formed through hydrogen bonds and weak π-π stacking interactions.

Synthesis,Crystal Structure and Electrochemistry Properties of a Cobalt(Ⅱ) Complex Based on Asymmetry Schiff Base Ligand

A new cobalt（II） complex [Co（NO2-salen）2]·1.5H2O containing mono acetalization Schiff base ligand（NO2-salen = N-5-nitro-salicylideneamino ethanato） has been prepared through one-pot template condensation, and has been structurally characterized by elemental analysis, IR spectra and X-ray diffraction. It is formulated as C18H23CoN6O7.5, crystallizes in the hexagonal system, space group of R-3c with α = 25.895（18）, b = 25.895（18）, c = 35.075（6）, γ = 120o, V = 20368（3） and Z = 36. The ligand of 5-nitrosalicylaldehyde-ethylene-diamine takes unusual mono asymmetry mode. The Co（II） ion exhibits a coordination number of six, and assumes a distorted octahedral geometry with a N2O4 donor set. The neutral monomeric units of [Co（NO2-salen）2]·1.5H2O are linked into a one-dimensional（1D） structure via the intermolecular hydrogen bonds and weak π-π stacking interactions. Cyclic-voltammetry measurement reveals the oxidation and reduction processes for the complex are irreversible in nature.

Synthesis,Crystal Structure and Characterization of a Cobalt Coordination Polymer:[Co(bib)(L)]·0.5H_2O

The title coordination polymer, [Co（bib）（L）].0.5H2O 1 （bib = 1,1＇-（1,4-butanediyl）bis（imidazole） and L = 4,4＇-oxy（bisbenzoate） has been hydrothermally synthesized and characterized by IR and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group Cc with a = 8.8568（5）, b = 19.936（1）, c = 26.209（2） γ, y = 97.510（1）°, V= 4587.8（5） A3, Z = 8, CoC24H23N4O5.5, Mr = 514.39, Dc = 1.489 g/cm3, F（000） = 2128, μ（MoKa） = 0.795 mm^-1, R = 0.0419 and wR = 0.1002. Compound 1 exhibits a rare two-fold interpenetrating CdSO4 type topology. The O-H...O hydrogen bonds stabilize the structure of 1.

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.

Synthesis, Crystal Structure and Properties of a Dinuclear Cobalt(Ⅱ) Complex [Co_2(α-furacrylato)_4(Phen)_2(H_2O)]·C_2H_5OH

A dinuclear cobalt（II） complex [Co2（a-furacrylato）4（Phen）2（H20）]＇C2HsOH has been synthesized with a-furacrylic acid and 1,10-phenanthroline as the ligands, and its crystal structure was determined. The crystal is of monoclinic system, space group C2/c with a = 1.07388（8）, b = 2.4300（2）, c = 1.86708（14） nm, β= 104.3830（10）°, V= 4.719.4（7） nm3, Dc = 1.503 g/cm3, Z = 2, F（000） = 2196, GOOF = 1.053, the final R = 0.0343 and wR = 0.0883. The crystal structure shows that two neighboring cobalt（II） ions are linked by the bridging coordination of two a-furacrylic acid anions and one water molecule, and their end positions are respectively coordinated with two 1,10-phenanthroline molecules and two a-furacrylic acid anions, forming a dinuclear structure. Both cobalt（II） ions adopt hexa-coordinated distorted octahedral geometry. The electrochemical and fluorescence properties of the title complex are also discussed.

Syntheses and Crystal Structures of Cobalt(II) Chloride Complexes of 1,3-Bis(pyridyl-4-ylthio)propan-2-one

Reactions of 1,3-bis（pyridyl-4-ylthio）propan-2-one L and COCl2·6H2O under different conditions gave two new cobalt（Ⅱ）-chloride-L complexes with distinct structures. Complex [Co（L）2Cl2]·0.5CH3OH}n 1 prepared by solvothermal treatment is a 3D network, whereas complex {[Co3（L）2Cl6（DMF）4]·2CH3OH·H2O} 2 obtained in DMF-diethyl ether system is a discrete acyclic trimer. Crystal data for 1： space group lbca, a = 15.993（4）, b = 18.454（5）, c = 21.506（6）A, V= 6347（3） ,A^3, Z = 8, Dc = 1.462 g/cm^3,μ = 1.005 mm^-1, F（000） = 2864, C26.5H26Cl2CoN4O2.5S4, Mr = 698.58, the final R = 0.0499 and wR = 0.1024. Crystal data for 2： space group P1^-, a = 9.9177（6）, b = 11.0871 （4）, c = 15.5490（12） ,A, α = 83.1834（14）,β = 88.910（13）, γ = 71.096（ 11 ）°, V = 1605.8（2） A^3, Z = 1, Dc = 1.362 g/cm^3,μ= 1.194 mm^-1, F（000） = 677, C40H62Cl6Co3N8O9S4, Mr = 1316.71, the final R = 0.0666 and wR =0.1575.

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-norbor- nene-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 α = 13.0430（13）, b = 21.014（2）, c = 7.5151（7） ？, β = 102.319（2）o, V = 2012.4（3） A3, 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 stabilityand electrochemical properties have studied in this paper.

Synthesis and Crystal Structure of an Ion-pair Supramolecular Associate 2,9-Diformyl-1,10-phenanthrolinebis-(2,6-dimethylanil)cobalt(Ⅱ) Perchlorate

2,9-Diformyl-l, 10-phenanthrolinebis（2,6-dimethylanil）cobalt（Ⅱ） perchlorate was synthesized and demonstrated to be [COL2][ClO4]2 by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group C2/c with a = 22.294（4）, b = 15.122（3）, c = 20.640（4） A, β = 119.618（4）°, V = 6048.9（19） A^3, C63H52Cl2CoN9O9, Mr= 1208.97, F（000） = 2504, De= 1.328g/cm^3, Z = 4, μ= 0.436, the final R = 0.0712 and wR = 0.1718 for 1734 observed reflections （I 〉 2σ（I））. In its solid state the helical polymeric chains are supramolecularly associated through intermolecular and interionic hydrogen bonding interactions.

Syntheses,Crystal Structures and Electrochemical Properties of Supramolecular Complexes [M_4L_(12)]·(HPO_4)·(PO_4)_2(L=2,2'-Dibenzimidazole,M=Co and Ni)

Two novel supramolecular complexes,[M4L12]·（HPO4）·（PO4）2（L = 2,2＇-dibenzi-midazole,M = Co and Ni） were synthesized by the hydrothermal method and characterized by elemental analysis,IR,UV,and TG-TGA,and the crystal structures were determined by single-crystal X-ray diffraction.The results showed that both of them belong to the cubic system and space group I 4 3d.Crystal parameters of C168H121Co4N48O12P3（1）：a = b = c = 2.5104（6） nm,V = 15.820（7） nm3,Mr = 3332.75,Z = 4,Dc = 1.399 Mg/m3,μ = 0.521 mm-1,F（000） = 6852,S = 1.011,the final R = 0.0248 and wR = 0.0663 for 2120 observed reflections（I 2σ（I）） and R = 0.0315 and wR = 0.0706 for all data.Crystal parameters of C168H121Ni4N48O12P3（2）：a = b = c = 2.4977（5） nm,V = 15.581（5） nm3,Mr = 3331.87,Z = 4,Dc = 1.420 Mg/m3,μ = 0.587 mm-1,F（000） = 6868,S = 1.074,the final R = 0.0443 and wR = 0.1364 for 1774 observer reflections（I 2σ（I）） and R = 0.0647 and wR = 0.1492 for all data.Each of them consisted of four M（II） cations,twelve 2,2＇-dibenzimidazole ligands,one monohydrogen phosphate anion and two phosphate anions in the single cell.The central M（II） cation,coordinated with six alkaline nitrogen atoms from three 2,2＇-dibenzimidazole ligands,displayed the expected distorted-octahedral geometry.The 3D supramolecular system was formed by the hydrogen bond N-H...O and π-π stacking interaction between neighboring single cells.Complex 1 showed two irreversible single-electron reduction processes of the central metal ion at-0.06 and-0.42 V in DMF solution.

Synthesis,Crystal Structure and Characterization of a Cobalt Coordination Polymer:[Co(suc)(L)]_n

The title complex, [Co（suc）（L）], 1 （L = 2-phenyl-lH-1,3,7,8-tetraazacyclopenta- [1]phenanthrene and H2suc = succinic acid） has been hydrothermally obtained and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. It crystallizes in orthorhombic, space group Pcca with a = 13.936（3）, b = 9.918（2）, c = 28.670（6）A, V = 3962.4（14）A^3, Z = 8, CoC23H16N4O4, Mr = 471.33, Dc = 1.580 g/cm^3, F（000） = 1928,μ（MoKa） = 0.907 mm^-1, R = 0.0543 and wR = 0.1336. Compound 1 exhibits one-dimensional chain structures which are further stacked by π-π interactions to give a supramolecular layer. Finally, the N-H...O hydrogen bonds between the nitrogen atom of L and carboxylate oxygen atom stabilize the structure of 1.

Syntheses and Crystal Structures of Cobalt(II) and Nickel(II) Coordination Polymers with 3-Aminobenzoic Acid Ligand

Two coordination polymers, [ML2]n （M = Co （1）, Ni （2）, L = 3-aminobenzoic acid anion）, were synthesized by hydrothermal reaction, and their crystal structures were determined by X-ray diffraction analysis. Both compounds crystallize in monoclinic, space group P21/n with a = 8.8029（8）, b = 4.5297（4）, c = 15.2002（14）A°, β= 105.6280（10）°, C14H12CoN2O4, Mr= 331.19, Z= 2, V = 583.69（9）A°^3 Dc= 1.884 g/cm^3,μ=1.490 mm^-1, F（000） = 338, R = 0.0234 and wR = 0.0679 for 1337 observed reflections （I 〉 2σ（I）） for 1, and a = 8.7501（7）, b = 4.5191（4）, c = 15.1448（12） A°,β = 105.7730（10）° C14H12 NiN2O4, Mr = 330.97, Z = 2, V = 576.31（8）A°3, Dc = 1.907 g/cm^3,μ = 1.703 mm^-1, F（000） = 340, R = 0.0206 and wR = 0.0572 for 1209 observed reflections （I 〉 2σ（I）） for 2. In the title complexes, the M （Ⅱ） ion presents an octahedral geometry with four oxygen donors in the equatorial positions and two nitrogen donors in the axial positions. Each of the complexes has a two-dimensional network structure that is formed by the bridging of the ligand in a μ3-bridging mode via its amino and carboxyl groups.

Synthesis, Crystal Structure, and Fluorescent and Thermal Stability Properties of Two New Cobalt(Ⅱ) Complexes with 2,2’-Bipy as Ligand

Two new cobalt(Ⅱ)complexes[Co2(2,2?-bipy)2(dpa)2(H2O)5]·4H2O(1)and Co(2,2?-bipy)3(SO4)]·7.5H2O(2)have been synthesized with diaphonic acid(H2dpa)and 2,2?-bipyridine(2,2?-bipy)as ligands.In 1,two neighboring cobalt(Ⅱ)ions are linked together by one bridging diaphonic acid group,forming an asymmetric dinuclear structure.1 crystallizes in triclinic,space group P1 with a=9.825(6),b=13.007(8),c=19.586(1)A,α=80.773(1)o,β=77.065(1)o,γ=85.902(1)o,Mr=431.4,V=2406.5(3)A^3,Dc=1.48 g/cm^3,Z=2,μ(Mo Kα)=0.767 mm-1,F(000)=1112,the final R=0.0379 and wR=0.0862.The central cobalt(Ⅱ)ions in 1 and 2 are coordinated with six atoms,forming distorted octahedral coordination geometry.The fluorescence and thermal stability properties of 1 and 2 are also reported.

Synthesis,Crystal Structure and Characterization of a Cobalt Coordination Polymer:[Co(1,4-ndc)(L) (H_2O)]n

The title coordination polymer, [Co（1,4-ndc）（L）（H2O）]n 1 （1,4-H2ndc = 1,4-na- phthalenedicarboxylic acid and L =1-（5-（1H-imidazol- 1-yl）pentyl）- 1H-imidazole） has been hydrothermally synthesized and characterized by IR and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 12.4333（12）, b = 13.2963（13）, c = 13.4678（13）A, α =β = 90°, y =107.302（2）°, V= 2125.7（4）A^3, Z = 4, CoC22H22N4O5, Mr = 481.37, De = 1.504 g/cm^3, F（000） = 996, μ（MoKa） = 0.850 mm^-1, R = 0.0472 and wR = 0.0984. Compound 1 exhibits a two-dimensional layer structure. The O-H...O and C-H...O hydrogen bonds stabilize the structure of 1.