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, 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 and Crystal Structure of a Seven-coordinate Cadmium(Ⅱ) Complex

The reaction of 4-hydroxybenzoic acid (H2L),4, 4-diaminodiphenylmethane (DADPM) and Cd(NO3)2?H2O in methane/water gave rise to a seven-coordinate Cd(Ⅱ) complex [Cd2(HL)4(H2O)6]?H2O which has been characterized by single-crystal X-ray diffraction. The complex crystallizes in the orthorhombic system, space group Pna21 with unit cell parameters: a = 10.3352(3), b = 12.0481(3), c = 28.2016(1) ? V = 3511.65(13) 3, Z = 4, C28H36Cd2O20, Mr = 917.37, Dc = 1.735 g/cm3, F(000) = 1840, (MoK? = 1.29mm-1. The final R and wR are 0.0536 and 0.1086 for 4898 observed reflections with I ≥ 4(I). The Cd(Ⅱ) is seven-coordinated in a distorted pentagonal bipyramidal geometry. The inter-molecular hydrogen bonds lead to the formation of a two-dimensional layer structure.

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 P2Jc with a = 11.481 （2）, b = 1 8.094（4）, c = 8.5198（17） ]°, β= 102.26（3）°, V = 1729.5（6） ,/k3, Z = 4, Dc = 1.759 g/cm3, F（000） = 932, p = 1.422 mm-1, R = 0.0368 and wR = 0.0893. In 1, the Cu（ll） 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.

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 Cadmium(Ⅱ) Coordination Polymer with Ethylenediaminetetraacetic Acid

A new cadmium（Ⅱ） coordination polymer,namely,[KCd2（edta）I]n（1,H4edta = ethylenediaminetetraacetic acid）,has been prepared and structurally characterized by single-crystal X-ray diffraction.Crystallographic data for 1：C10H12Cd2IKN2O8,Mr = 679.02,monoclinic,space group P21/n,a = 9.870（5）,b = 8.989（4）,c = 19.082（10） ,β = 104.581（10）o,V = 1638.5（13） 3,Z = 4,Dc = 2.753 g/cm3,μ = 4.776 mm-1,F（000） = 1272,the final R = 0.0473 and wR = 0.1311 for 2846 observed reflections with I 〉 2σ（I）.Polymer 1 features a 2-D layered structure,in which each edta4-ligand chelates/bridges five adjacent six-/seven-coordinated Cd（Ⅱ） centers with all ten donors（eight oxygen and two nitrogen） involved with coordination.Additional iodide I-ions as counterions are bound to the Cd（Ⅱ） centers in a terminal mode and the potassium K＋ ions are located in the layers and surrounded by O and I atoms from neighboring environment.The thermal stability of 1 has been discussed.

Synthesis and Crystal Structure of a Cadmium(Ⅱ) Coordination Polymer:[Cd_2Cl_4(bpme)]_n·n(2H_2O)

A novel coordination polymer, [Cd2Cl4（bpme）]n·n（H2O） （1, bpme=2,5-bis（be-nzoimidazol-2-yl）pyrazine）, has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal of the complex belongs to the triclinic system, space group P , with a=7.0737（9）, b=8.7886（11）, c=9.4561（12） , α=105.3580（10）, β=94.981（2）, γ=96.879（2）°, V=558.46（12） 3, Mr=714.97, Z=1, F（000）=346, Dc=2.126 g/cm3, μ=2.412 mm-1, T=296（2） K, S=1.057, R=0.0533 and wR=0.1480. According to the structural analysis, the Cd（Ⅱ） ion adopts a slightly distorted six-coordinated octahedral geometry. The Cd（Ⅱ） atoms are bridged by four Cl atoms along the a direction, forming infinite straight chains which are further constructed to generate 2D network layer structures through the μ4-N bpme ligand in the b direction, and such 2D network layer structures finally form a novel three-dimensional infinite supramolecular framework through weak π-π stacking between two network layers and hydrogen bonds.

Synthesis and Crystal Structure of a 1-D Chain Coordination Complex {[Mn_2(HCAM)_3(H_2bipy)]·5H_2O}_n

The 1-D chain coordination complex of {[Mn2（HCAM）3（H2bipy）]·5H2O}n （H3CAM = 4-hydroxypyridine-2,6-dicarboxylic acid, bipy = 4,4＇-bipyridine） has been synthesized by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid, 4,4＇-bipyridine and manganese carbonate under hydrothermal conditions, and its crystal structure was determined by X-ray diffraction method The crystal belongs to the monoclinic system, space group P21/n with a = 10.110（2）, b = 20.159（4）, c = 17.861（4）A,β = 99.67（3）°, V = 3.5884（12） nm3, Mr= 901.47, Z = 4, Dc= 1.669 g.cm^-3, μ= 0.798 mm^-1, F（000） = 1840, the final R = 0.0713 and ωR = 0.1853. The complex forms a 1-D chain bridged by HCAM, protonated 4,4-bipyridines link the 1-D chains to construct 2-D networks via N-H...O hydrogen bonds, and networks are further extended via π-π stacking and hydrogen bonds into 3-D supramolecular framework.

Synthesis and Crystal Structure of a Co(Ⅱ) Complex with Taurine-5-methyl-2-hydroxyisophthalaldehyde Schiff Bases [Co(C_(13)H_(16)N_2O_7S_2)(H_2O)_3]_2·H_2O

The title complex [CoL（H20）3]2·H2O （C26H46N4O21S4CO2）, where L = taurine-5- methyl-2-hydroxyisophthalaldehydes, has been synthesized and characterized by IR and X-ray diffraction analysis. The crystal of the complex belongs to the triclinic system, space group P1, with a = 11.197（4）, b = 13.309（5）, c = 14.486（5） ]A, a = 78.827（13）,β = 70.547（11）, γ = 81.058（13）°, Mr = 996.77, S = 1.08, V= 1987.2（13） A3, Z = 2, Dc = 1.666 g/cm3, F（000） = 1032,μ = 1.131 mm^-1, R = 0.0633 and wR = 0.1293. According to the structural analysis, the Co（ Ⅱ ） ion adopts a slightly distorted six-coordinated octahedral geometry. One N atom of the Schiff base of each molecule was hydrogenated to form hydrogen bond with O atom. Two coterminous molecules packed in one crystal water molecule are linked by intermolecular hydrogen bonds, thus generating an infinite chain constructed by hydrogen bonds.

Hydrothermal Synthesis and Crystal Structure of a Novel Catena Co(Ⅱ) Complex Bridged by Biphenyl- 2,2′-dicarboxylate Divalent Anion

The title complex, [Co_2(bpdc)_2(bim)_4]_n(bpdc=biphenyl-2,2′-dicarboxylate dianion, bim=benzimidazole), was synthesized in a aqueous solution and its crystal structure was determined by means of X-ray diffraction. There are two different coordinated Co(Ⅱ) centers in the complex. The Co1 center has a deformed trigonal-bipyramidal geometry, while the Co2 center possesses a tetrahedral geometry. In addition, the two different coordination modes of bpdc ligands act as two kinds of bridges to link Co1 and Co2, resulting in a catena chain.

Synthesis, Crystal Structure and Electrochemical Properties of One-dimensional Chain Coordination Polymer [Co(II)(C_6H_5CH=CHCOOH)_2(4,4′-bipy)(H_2O)_5]_n

A one-dimensional chain coordination polymer [Co（Ⅱ）（C6H5CH--CHCOOH）2（4,4＇- bipy）（H20）5]n has been synthesized with cinnamylic acid, 4,4＇-bipy and cobaltous chloride as raw materials. Crystal data for this complex： monoclinic, space group P21/c, a = 1.1481（3）, b = 1.1230（2）, c = 1.1759（3） nm, β = 97.054（4）^o, V= 1.5046（6） nm^3, Mr= 617.50, Dc = 1.363 g/cm^3, Z = 2, ,u（MoKa） = 0.627 mm^-1, F（000） = 646, S = 1.062, R 0.0443 and wR = 0.1178. The crystal structure shows that two neighboring cobalt（ID ions are linked together by one 4,4＇-bipy, and the whole complex molecule adopts a one-dimensional chain structure. Each cobalt（H） ion is coordinated with two nitrogen atoms from two 4,4＇-bipy molecules and four oxygen atoms from four water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were analyzed by combining with the crystal structure.

Synthesis and Crystal Structure of Bis-{N-[2-(6-ethylpyridyl)]-salicylideneiminato} Cobalt(Ⅱ)

The title complex 1, C28H26CoN4O2, crystallizes in the triclinic system, space group P with a = 9.506(3), b = 9.506(3), c = 14.837(5) ? a = 106.397(5), b = 106.012(5), g = 91.889(6), V = 1217.7(7) 3, Z = 2, Dc =1.390 g/cm3, Mr = 509.46, F(000) = 530, m(MoKa) = 0.738 mm-1, the final R = 0.0359 and wR = 0.0951 for 4275 observed reflections with I > 2s(I). The complex adopts a distorted tetrahedral coordination sphere around the cobalt atom.

Ionothermal Syntheses and Crystal Structures of Two Cobalt(Ⅱ) Compounds:Co(2,2'-bpy)_2Br_2 and Co(1,10-phen)_2Br_2

Two cobalt（Ⅱ） compounds,Co（2,2-bpy） 2 Br 2 （1,2,2-bpy=2,2-bipyridyl） and Co（1,10-phen） 2 Br 2 （2,1,10-phen=1,10-phenanthroline）,have been prepared under ionothermal reactions using the 1-propyl-3-methylimidazolium bromide ionic liquid solvent.Single-crystal X-ray analyses reveal that 1 crystallizes in a monoclinic space group P2 1 /c,with a=8.5509（13）,b=14.804（2）,c=15.650（2）,β=97.119（2） o,V=1965.8（5） 3,Z=4,C 20 H 16 Br 2 N 4 Co,M r=531.12,D c=1.795 g/cm 3,μ=4.950 mm-1,F（000）=1044,the final R=0.0467 and wR=0.0736 for 2291 observed reflections with I 2σ（Ⅰ）.Complex 2 crystallizes in a monoclinic space group P2 1 /n,with a=10.4237（8）,b=16.8657（12）,c=12.4945（9）b,β=102.110（1） o,V=2147.7（3） 3,Z=4,C 24 H 16 Br 2 N 4 Co,M r=579.16,D c=1.791 g/cm 3,μ=4.540 mm-1,F（000）=1140,the final R=0.0431 and wR=0.1042 for 3470 observed reflections with I 2σ（Ⅰ）.The mononuclear molecules of 1 are linked by the C-H···Br hydrogen bonds and π-π interactions to form a three-dimensional supramolecular framework structure.The C-H···Br hydrogen bonds and π-π interactions link the mononuclear molecules of 2 to give a two-dimensional layer structure.

Synthesis and Crystal Structure of a Co(II) Complex with Schiff Base and Imidazole Ligand

The title compound, [Co（C3H4N2）2（C22H18N2O4）]·5H2O （Mr = 659.56）, has been prepared and its crystal structure was determined by X-ray diffraction method. The crystal belongs to monoclinic, space group P21/n, a = 9.6808（2）, b = 26.7204（5）, c = 12.7993（3） A, β = 100.9340（10）°, V= 3250.75（12） A^3, Z = 4, Dc = 1.348 g/cm^3,μ = 0.586 mm^-1, F（000） = 1380, S = 1.131, R = 0.0689 and wR = 0.1883 for 4782 observed reflections （Ⅰ 〉 2σ（Ⅰ））. The title crystal consists of Co（Ⅱ） complex and lattice water molecules. The Co（Ⅱ） complex assumes a distorted octahedral coordination geometry, formed by one Schiff base dianion phenylenediamine-3-methoxysali-cylaldehyde and two imidazole ligands. The π-π stacking interaction occurs between nearly parallel benzene rings of the neighboring complexes.

Synthesis, Crystal Structure and Thermal Stability Properties of the Supramolecular Complex [Co(phen)_3][(C_6H_5)_2C(OH)COO]_2·7H_2O

One new cobalt complex [Co（phen）3][（C6Hs）2C（OH）COO]2·7H2O with benzeneacetic acid （BAA）, 1,10-phenanthroline and cobaltous perchlorate has been synthesized by means of solvent method. It crystallizes in the triclinic system, space group P^-1, with a = 1.14181（13）, b = 1.64417（18）, c = 1.65342（18） nm, α = 74.2830（10）, β= 84.4490（10）, γ = 74.9430（10）°, V = 2.8842（6） nm^3, Dc = 1.359 g/cm^3, Z = 2, F（000） = 1234, R = 0.0621 and wR = 0.1673. The crystal structure shows that the cobalt ion is coordinated with six nitrogen atoms from three 1,10-phenanthroline molecules, giving a distorted octahedral coordination geometry. There are a lot of hydrogen bonds in the complex, from which a two-dimensional network is constructed. The result of TG analysis shows that the title complex is stable below 130.0 ℃.

Synthesis,Crystal Structure and Thermal Stability of a One-dimensional Chain Cobalt Coordination Polymer [Co(4,4'-bipy)(2,4,6-TMBA)_2(CH_3CH_2OH)_2]_n

A one-dimensional chain cobalt（Ⅱ） coordination polymer with 2,4,6-trimethyl- benzoic acid, 4,4′-bipyridine and cobalt perchlorate anhydrous has been synthesized and characterized in the mixture solvent of water and alcohol. Crystal data for this complex： monoclinic, space group C2/c, a = 2.3805（8）, b = 1.1464（4）, c = 1.5807（5） nm, y = 128.435（4）°, V= 3.3791（18） nm^3, Dc = 1.246 g/cm^3, Z = 4, F（000） = 1340, final GooF = 1.009, R = 0.0504 and wR = 0.1287. Structural analysis shows that the cobalt ion is coordinated with two nitrogen atoms of one 4,4′- bipyridine molecule and four oxygen atoms from two 2,4,6-trimethylbenzoic acid molecules and two alcohol molecules, giving a distorted octahedral coordination geometry. The result of TG analysis indicates that the title complex is stable till 200 ℃.

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.

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.