Hydrothermal Syntheses and Crystal Structures of Three Lanthanide(Ⅲ)Complexes Based on Carboxyl Derivatives of 1,10-Phenanthroline

Three lanthanide（III） complexes [Ln（4-NCP）（1,4-BDC）]n·xn H2O（Ln = Pr（1）, Sm（2）, Nd（3）. 4-HNCP = 2-（4-carboxyphenyl）imidazo（4,5-f）（1,10）phenanthroline, 1,4-H2 BDC = benzene-1,4-dicarboxylic acid） have been hydrothermally synthesized and characterized via elemental analysis, infrared spectrometry and single-crystal X-ray diffraction. Structural analyses revealed that complexes 1~3 possess similar porous three-dimensional frameworks with the point symbol {4^（12）·6~3}. Meanwhile, complexes 1~3 exhibit excellent thermal stabilities and complex 2 exhibits characteristic luminescent property.

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.

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.

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 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 ■ with a=9.825（6）,b=13.007（8）,c=19.586（1）?,α=80.773（1）o,β=77.065（1）o,γ=85.902（1）o,Mr=431.4,V=2406.5（3）?3,Dc=1.48 g/cm3,Z=2,μ（MoKα）=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.

Syntheses aod Crystal Structures of Rare Earth Complexes with Adamantanecarboxylic Acid, [LnL_3(HL)(H_2O)]_2·2EtOH·2H_2O (Ln=Nd (1), La (2))

The title complexes （LnL3 （HL） （H2O） ]2· 2EtOH·2H2O （Ln= Nd （1）, La （2）, HL=adamantanecarboxylic acid） were prepared and determined by single-crystal X-ray diffraction. Both complexes crystallize in triclinic system with space group P 1^-, cell parameters are： complex （1） a = 1.0556（2） nm, b =1.4913（3） nm, c = 1.4920（3） nm, a = 106.26 （3）°, β=93.51（3）°, γ=97.23（3）°, V=2.2253 （5） nm^3, Dcal=1.409 g · cm^-3, Z = I , F （ 000 ） = 990, μ（Mo Kα） = 1. 225 mm^-1, M, = 1884.50; complex （2） a = 1.0453（2） nm, b = 1.4971（3）nm, c = 1.5052（3） nm, α = 106.07（3）°, β =93.58 （3）°, γ=97.56（3）°, V=2.2391（5）nm^3, Dcal= 1.397 g·cm^-3, Z = 1, F（000） =984, μ（Mo Kα） = 1.015 mm^-1, Mr= 1877.88. The final R and wR are 0. 0396 and 0. 1062 for 8589 （1 ≥ 2σ （I）） observed reflections for complex （1）, 0.0505 and 0. 1344 for 8417 （ 1 ≥ 2σ （1） ） observed reflections for complex （2）, respectively. The crystals are consisted of a binuelear molecule. The coordination geometry of the Ln（ Ⅲ ） ion can be described as trieapped trigonal prism.

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.

Syntheses and Crystal Structures of Two New Main Group Metal Complexes (M = Al, Bi) with the Substituted p-Hydroquinones

The title complexes [Al（Hcah）（H2O）2]·2H2O （A） and [Bi（Hcah）（H2O）]n （B）, where H4cah = 2-[N,N-bis（carboxymethyl）aminomethyl] hydroquinone, have been synthesized and characterized using X-ray single-crystal structure determination, IR and elemental analysis. Both complexes crystallize in the monoclinic system, space group P21/c with a = 7.8660（16）, b = 10.096（2）, c = 19.053（4） and β = 93.50（3）° for A; and those for B： a = 9.2348（18）, b = 7.9061（16）, c = 17.141（3） and β = 102.64（3）°. In addition, further investigation revealed that the central Al（III） ion in the mononuclear complex A is in a distorted octahedral coordination geometry, while structural analysis reveals that the Bi（III） ion is in a distorted pentagonal bipyramid, forming a 2-D polymeric complex B, and the coordination network is a 2D 4.82 net. The TG analyses of A indicate two steps of water loss.

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.

Synthesis and Crystal Structure of a Binuclear Gadolinium（Ⅲ） Complex Bridged by Cucurbit[6]uril

A new cucurbit[6]uril bridsed binuclear complex {[Gd（H2O）6]2[Q6（H2O）]}C16·4H2O, where Q6 represents cucurbit[6]uril, has been synthesized and characterized by X-ray diffraction. The crystal structure shows that the complex has an extended cucurbit[6]uril-bridged structure consisting of two gadolinium（Ⅲ） ions, in which each gadolinium（Ⅲ） ion is coordinated with two neighboring carbonylic oxygen atoms of Q6 and six oxygen atoms of water molecules that leans toward one side of the portal. One disordered guest water molecule resides in the Q6 molecule cavity and occupies two different positions. Hydrogen bonds assemble the complcx to threedimensional supramolecular structure.

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.

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 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.

Crystal Structure of Binuclear Manganese(Ⅲ) Complex with Schiff-base Ligand,〔Mn_2(C_(22)H_(22)N_2O_2)_2(EtOH)_2 (bipy)〕(ClO_4)_2

The title complex, [Mn2L2(EtOH)2 (bipy )](ClO4)2 (L=N,N'-ethylenebis (1-phenyl-3-imino-1-butanonato), bipy = 4, 4'-bipyridine] crystallizes inmonoclinic system, space group P21/c with a= 12. 63O(5), b=13- 151 (2), c=18. 3773001 reflections The two [MnL(EtOH)]+ units are joined by one 4, 4'-bipyridine molecule to form a centrosymmetric binuclear complex cation [Mn2L2(EtOH)2 (bipy]2+. The coordination geometry around Mn atoms is a distorted octahe-dron with equatorial plane N2O2 from the Schiff base ligand L.

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 and Crystal Structure of trans(N)-(1,10-Phenanthroline)-bis (DL-Al aninato)-Cobalt( Ⅲ ) Chloridetrihydrate

The title compound was synthesized by the reaction of cis-[Co(phen)2Cl2]Cl·3H2O with DL-alanine at pH = 8, and isolated using a column chromatographic method. Its crystal structure was determined. The crystal structure belongs to mono-clinic system, space group P21/c, with a = 0. 9549(6) nm, b=2.3746(8) nm, c= 1.0782(4) nm, β=114.13(3)°? Z = 4, Dc= 1. 50 g/cm3. The final refinement converged to R = 0. 047 for 3246 independent observed reflections. In the octahedral coordination sphere formed by the cobalt atom and the coordinate atoms, N, O of DL-alan-inato ligands are in the configuration of trans-N ,N form.

Synthesis and Crystal Structure of Novel Dimer of Bismuth(Ⅲ) Complex with Dithiotetrahydropyrrolocarbamate: [Bi(S_2CNC_4H_8)_2(NO_3)]_2

A novel dimer of the bismuth(Ⅲ) complex with dithiotetrahydropyrrolocarbamate, [Bi(S_2CNC_4H_8)_2·(NO_3)]_2, was synthesized and the crystal structure was determined by X-ray single crystal diffraction. The crystal belongs to a monoclinic system with space group P2_1/n, a=0.64718(13) nm, b=2.6738(6) nm, c=1.0423(2) nm, β=106.384(3)°, Z=4, V=1.730(3) nm^3, D_c=2.163 g/cm^3, μ=10.682 mm^(-1), F(000)=1072, R=0.0329, wR=0.0659. The structure shows a distorted pentagonal bipyramidal configuration with the seven-coordinated central Bi atom. In the crystal, the molecular packing in the unit cell reveals that the two adjacent molecules are symmetrically linked each other in the dimer by virtue of a couple of Bi-S interaction.

Syntheses and Structures of Two Isomorphous Metal-organic Coordination Complexes Based on 4-Pyrimidin-5-ylbenzoic Acid

The reactions of 4-pyrimidin-5-ylbenzoic acid （HL） with Co（NO3）2·6H2O and Ni（NO3）2·6H2O gave rise to two isomorphous mononuclear coordination complexes, namely, [CoL2（H2O）4] （1） and [NiL2（H2O）4] （2）. Both compounds were characterized by IR spectroscopy and single-crystal X-ray diffraction. X-ray crystallographic analyses reveal that they crystallize in monoclinic, space group P21/n. In the crystal structures of these two complexes, only one nitrogen atom of L coordinates to the metal center, and neither carboxylate group nor another nitrogen atom of L links to Co（Ⅱ） or Ni（Ⅱ）. 2D Layers with significant hydrogen bonds can be observed, and they are further linked by L to form a 3D supramolecular network. Nitrogen atoms are not involved in forming hydrogen bonds, but carboxylic groups of the ligands play an important role in the configuration of this hydrogen-bond layer.