Crystal Structure of a New Triply‐Bridged Cobalt(III) Dimer with 2, 2′‐Dipyridylamine (dipyam), [Co2(μ‐OH)2(μ‐OAc)(OAc)2(dipyam)2]AcO·EtOH

The structure of [Co₂(μ‐OH)₂(μ‐OAc)(OAc)₂(dipyam)₂]AcO · EtOH ( 1 ) has been determined by single‐crystal X‐ray analysis. The cationic complex may be described as a “di(μ‐hydroxo)(μ‐acetato)dicobalt(III)” core with chelating 2, 2′‐dipyridylamine and monodentate acetate ligands. The coordination polyhedron around each cobalt atom is a distorted octahedral. The dimers are linked in the crystal by N‐H···O_{ionic AcO} and C‐H···O_{monodentate AcO} hydrogen bonds. Spectroscopic data are also presented.     

[Cu(bpp)2(bpdc)(H2O)2]×2H2O and [Cu(bpp)2](tdc)×7.5H2O的合成、晶体结构和热稳定性

在室温下, 由Cu(NO3)2 、1,3 -二（4 -吡啶基）丙烷(bpp)、4,4 ’ -联苯二甲酸(H2bpdc)和2,5-噻吩二甲酸(H2tdc)制备出两种新型铜( II)配位聚合物[Cu(bpp)2(bpdc)(H2O)2]n·2nH2O, 1 和[Cu(bpp)2]n·n(tdc) 7.5nH2O, 2。两个配位聚合物均为一维线型结构,铜原子均采取变形的八面体结构,在轴线方向上的两个水分子与铜原子存在较弱的配位作用。在配合物1中,两个bpdc羧酸根离子与铜原子配位,而2中的tdc羧酸离子没有与铜原子键合,只是作为反离子平衡电荷。在两个产物中, 配体bpp具有不同的构象。热重分析表明配合物1与2分别在110°C和160°C以下是稳定的。     

Koordinationspolymere 1, 2‐Dithiooxalato‐ und 1, 2‐Dithioquadratato‐Komplexe. Synthese und Strukturen von [BaCr2(bipy)2(1, 2‐dtox)4(H2O)2], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)2(H2O)2]·2H2O und [H3O][H5O2][Cu(cyclam)]3[Cu2(1, 2‐dtsq)3]2

Coordination Polymeric 1, 2‐Dithiooxalato and 1, 2‐Dithiosquarato Complexes. Syntheses and Structures of [BaCr₂(bipy)₂(1, 2‐dtox)₄(H₂O)₂], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)₂(H₂O)₂]·2H2₂, and [H₃O][H₅O₂][Cu(cyclam)]₃[Cu₂(1, 2‐dtsq)₃]₂ 1, 2‐Dithioxalate and 1, 2‐dithiosquarate ions have a pair of soft and hard donor centers and thus are suited for the formation of coordination polymeric complexes containing soft and hard metal ions. The structures of four compounds with building blocks containing these ligands are reported: In [BaCr₂(bipy)₂(1, 2‐dtox)₄(H₂O)₂] Barium ions and pairs of Cr(bipy)(1, 2‐dtox)₂ complexes form linear chains by the bisbidentate coordination of the dithiooxalate ligands towards Ba²⁺ and Cr³⁺. In [Ni(cyclam)(1, 2‐dtsq)]·2DMF short NÖH···O hydrogen bonds link the NiS₂N₄‐octahedra with C_2v‐symmetry to an infinite chain. In [Ni(cyclam)Mn(1, 2‐dtsq)₂(H₂O)₂]·2H₂O the 1, 2‐dithiosquarato ligand shows a rare example of S‐coordination towards manganese(II). The sulfur atoms of cis‐MnO₂S₄‐polyedra are weakly coordinated towards the axial sites of square‐planar NiN₄‐centers, thus forming a zig‐zag‐chain of Mn···Ni···Mn···Ni polyhedra. [H₃O][H₅O₂][Cu (cyclam)]₃[Cu₂(1, 2‐dtsq)₃]₂ contains square planar [Cu^II(cyclam)]²⁺ ions and dinuclear [Cu^I₂(1, 2‐dtsq)₃]^4— ions. Here each copper atom is trigonally planar coordinated by S‐donor atoms of the ligands. The Cu…Cu distance is 2.861(4)Å.     

Self‐assembly properties of Salamo‐type trinuclear Cu(II) and Co(II) complexes based on the regulation of H+/OHˉ

A novel naphthalenediol‐based bis(salamo)‐type tetraoxime compound (H₄L) was designed and synthesized. Two new supramolecular complexes, [Cu₃(L)(μ‐OAc)₂] and [Co₃(L)(μ‐OAc)₂(MeOH)₂]·4CHCl₃ were synthesized by the reaction of H₄L with Cu(II) acetate dihydrate and Co(II) acetate dihydrate, respectively, and were characterized by elemental analyses and X‐ray crystallography. In the Cu(II) complex, Cu1 and Cu2 atoms located in the N₂O₂ sites, and are both penta‐coordinated, and Cu3 atom is also penta‐coordinated by five oxygen atoms. All the three Cu(II) atoms have geometries of slightly distorted tetragonal pyramid. In the Co(II) complex, Co1 and Co3 atoms located in the N₂O₂ sites, and are both penta‐coordinated with geometries of slightly distorted triangular bipyramid and distorted tetragonal pyramid, respectively, while Co2 atom is hexa‐coordinated by six oxygen atoms with a geometry of slightly distorted octahedron. These self‐assembling complexes form different dimensional supramolecular structures through inter‐ and intra‐molecular hydrogen bonds. The coordination bond cleavages of the two complexes have occurred upon the addition of the H⁺, and have reformed again via the neutralization effect of the OH^?. The changes of the two complexes response to the H⁺/OH^? have observed in the UV–Vis and ¹H NMR spectra.     

Cu(OAc)2·H2O/NH2OH·HCl/CH3COONa: A Facile and Efficient Catalyst System for Copper‐catalyzed Azide–Alkyne Click Reactions in Water

A facile and efficient protocol has been developed for synthesis of 1,4‐disubstituted 1,2,3‐triazoles in good to excellent yields using Cu(OAc)₂·H₂O (0.5 mol%)/NH₂OH·HCl (0.5 mol%)/CH₃COONa (1.0 mol%) as the catalyst system. The presence of CH₃COONa (2 equiv) could ensure the in situ generation of Cu₂O as the active catalyst instead of CuCl from Cu(OAc)₂·H₂O (1 equiv)/NH₂OH·HCl (1 equiv). This protocol could be carried out in water under mild conditions.     

Complexes of Cu2(μ‐OAc)4(H2O)2 with 1,10‐Phenanthroline and Comparison with those of 2,2′‐Bipyridine. Crystal Structure of the Dimer [Cu(OAc)2(phen)](μ‐H2O)

The two complexes of composition Cu₂(OAc)₄(phen)(H₂O)₂ ( 1 ) andCu₂(OAc)₄(phen)₂(H₂O) ( 2 ) have been synthesized and characterized by chemical analysis and IR and electronic spectroscopies. Compound 2 has the structure of a dimer with a phenanthroline molecule and two monodentate acetate groups coordinated to each copper atom and a water molecule as the only bridging ligand between them. Each copper atom has a distorted square‐planar pyramidal coordination, determined by two oxygen atoms at 1.94(3) and 1.959(3) Å, two nitrogen atoms at 2.023(4) Å and the oxygen atom of the bridging water molecule at 2.289(2) Å. The distance between the two copper atoms is of 4.29 Å and the angle Cu(1)‐O(3)‐Cu(1A) 139.2(2)°. The water molecule is involved in two intramolecular hydrogen bonds with non coordinated oxygen atoms. The distance between the molecules of phenanthroline is 3.75 Å. Magnetic and EPR results for Cu₂(OAc)₄(phen)(H₂O)₂ ( 1 ), Cu₂(OAc)₄(phen)₂(H₂O) ( 2 ), Cu₂(OAc)₄(bipy) ( 3 ) and Cu₂(OAc)₄(bipy)₂(H₂O)₂ ( 4 ) have been analysed and compared. For 1 and 3 an antiferromagnetic dimer unit [Cu₂(μ‐OAc)₄] with 2J = ?325 and ?292 cm^?1, respectively, and other two copper atoms without significant magnetic interaction are present. Triplet signals are detected in the EPR spectra. In 2 and 4 there is no practically magnetic exchange and the orthorhombic signals are observed in the EPR spectra.     

Structural Study of Nickel(II), Copper(II), and Palladium(II) Complexes of 2‐Pyridineformamide 3‐Hexamethyleneiminylthiosemicarbazone

Reduction of 2‐cyanopyridine by sodium in the presence of 3‐hexamethyleneiminylthiosemicarbazide produces 2‐pyridineformamide 3‐hexamethyleneiminylthiosemicarbazone, HAmhexim. Complexes with nickel(II), copper(II) and palladium(II) have been prepared and the following complexes structurally characterized: [Ni(Amhexim)OAc], [{Cu(Amhexim)}₂C₄H₄O₄]·2DMSO·H₂O, [Cu(HAmhexim)Cl₂] and [Pd(Amhexim)Cl]. Coordination is via the pyridyl nitrogen, imine nitrogen and thiolato or thione sulfur atom when coordinating as the anionic or neutral ligand, respectively. [{Cu(Amhexim)}₂C₄H₄O₄] is a binuclear complex with the two copper(II) ions bridged by the succinato group in [Cu‐(HAmhexim)Cl₂] the Cu atom is 5‐coordinate and close to a square pyramid structure and in [Ni(Amhexim)OAc] and [Pd(Amhexim)Cl] the metal atoms are planar, 4‐coordinate.     

Synthesis,crystal structure and infrared spectra of Cu(II) and Co(II) complexes with 4,4′‐dichloro‐2,2′‐[ethylene dioxybis(nitrilomethylidyne)]diphenol

Novel 4,4′‐dichloro‐2,2′‐[ethylenedioxybis(nitrilomethylidyne)]diphenol (H₂L) and its complexes [CuL] and {[CoL(THF)]₂(OAc)₂Co} have been synthesized and characterized by elemental analyses, IR, ¹H‐NMR and X‐ray crystallography. [CuL] forms a mononuclear structure which may be stabilized by the intermolecular contacts between copper atom (Cu) and oxygen atom (O3) to form a head‐to‐tail dimer. In {[CoL(THF)]₂(OAc)₂Co}, two acetates coordinate to three cobalt ions through Co? O? C? O? Co bridges and four µ‐phenoxo oxygen atoms from two [CoL(THF)] units also coordinate to cobalt ions. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and Characterization of Copper(II) and Zinc(II) Tricyanomethanide (tcm) Complexes with Di(2‐pyridyl)amine (dpyam) as Co‐ligands: [Cu(dpyam)(tcm)2], [Cu(dpyam)(tcm)(OAc)] and Zn(dpyam)2(tcm)2

Three new transition metal tricyanomethanide complexes [Cu(dpyam)(tcm)₂] ( 1 ), [Cu(dpyam)(tcm)(OAc)] ( 2 ) and Zn(dpyam)₂(tcm)₂ ( 3 ) were synthesized and characterized by single crystal X‐ray diffraction analysis. In 1 each copper(II) atom is coordinated to three tcm anions and one dpyam molecule to form a square pyramide geometry. In 2 the coordination geometry around the central metal is also square pyramidal, and each copper atom is surrounded by two tcm anions, one dpyam ligand and one OAc. Both 1 and 2 display a µ_1,5‐tcm bridged infinite chain structure. In 3 each zinc(II) atom is coordinated by two tcm anions and two dpyam molecules to form a distorted octahedral geometry. Different from the former two complexes, 3 shows a mononuclear structure. Magnetic susceptibility measurement in the range 2–300 K indicates that there are weak antiferromagnetic couplings between adjacent copper(II) ions in 1 (J=?0.03 cm^?1) and 2 (J=?0.11 cm^?1) respectively.     

Synthesis and Characterization of [Hg(sulfamethoxazolato)2]·2DMSO and[Cu2(μ‐CH3CO2)4(sulfamethoxazole)2]

[Hg(sulfamethoxazolato)₂]·2DMSO ( 1 ) and [Cu₂(CH₃COO)₄(sulfa‐methoxazole)₂] ( 2 ) can be obtained by the reaction of sulfamethoxazole with mercury acetate or copper acetate in methanol. The structures of the two complexes were characterized by single crystal X—ray diffractometry. Compound 1 consists of sulfamethoxazolato ligands bridging the metal ions building an unidimensional chain. Two solvent dimethylsulfoxide molecules are involved via N‐H···O hydrogen bridges. The mercury atom shows a linear primary coordination arrangement formed by two trans deprotonated sulfonamidic nitrogen atoms. The overall coordination around the metal atom may be regarded as a strongly distorted octahedron when the interactions of mercury with four sulfonamidic oxygen atoms [bond distances of 2.761(4) Å—2.971(4) Å] are also considered to build an equatorial plane and the N1 and N1′ atoms [bond distance of 2.037(5) Å] occupy the apical positions. Compound 2 is a dinuclear complex in which the copper ions are bridged by four syn‐syn acetate ligands which are related by a symmetry centre located in the centre of the complex. Each copper atom presents a nearly octahedral coordination where the equatorial plane is formed by four oxygen atoms and an isoxazolic nitrogen atom and the second copper atom occupy the apical positions.     

Mononuclear Co(III), Ni(II) and Cu(II) complexes of 2‐(2,4‐dichlorobenzamido)‐N'‐(3,5‐di‐tert‐butyl‐2‐hydroxybenzylidene)benzohydrazide: Structural insight and biological assay

A series of mononuclear metal complexes of Co(III), Ni(II) and Cu(II) with 2‐(2,4‐dichlorobenzamido)‐N′‐(3,5‐di‐tert‐butyl‐2‐hydroxybenzylidene)benzohydrazide ( LH ₃ ) have been synthesized and characterized using various physico‐chemical, spectroscopic and single crystal X‐ray diffraction techniques. Structural studies of [Co( LH )( LH ₂ )]·H₂O ( 4 ) revealed the presence of both amido and imidol tautomeric forms of LH ₃ , resulting in a distorted octahedral geometry around the Co(III) ion. [Ni( LH )(H₂O)]·H₂O ( 5 ) and [Cu( LH )(H₂O)]·H₂O ( 6 ) are isomorphous structures and crystallize in the monoclinic P2₁/c space group. The crystal structures of 4 , 5 and 6 are stabilized by hydrogen bonds formed by the enclathrated water molecules, C‐H···π and π···π interactions. Complexes along with the ligand ( LH ₃ ) were screened for their in vivo anti‐inflammatory activity (carrageenan‐induced rat paw edema method) and in vitro antioxidant activity (DPPH free radical scavenging assay). Metal complexes have shown significant anti‐inflammatory and antioxidant potential.     

Synthesis,Crystal Structures and Electrochemical Properties of Complexes [M(ImH)4(tfbdc)(H2O)] (M=Co,Ni)

The title complexes [M(ImH)₄(tfbdc)(H₂O)] ( 1 : M=Co; 2 : M=Ni) (ImH=imidazole, tfbdc=2,3,5,6‐tetrafluoroterephthalate) were synthesized by the reaction of M(OAc)₂·4H₂O, H₂tfbdc and ImH in water solution. The complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis, cyclic voltammetry and X‐ray single crystal structure analysis. Structural analysis reveals that 1 and 2 possess isostructure: monoclinic, P2₁/c, Z=4. M(II) ion in complexes 1 and 2 has a distorted octahedral geometry coordinated by one oxygen atom from water, one oxygen atom from tfbdc^2? and four nitrogen atoms from ImHs. They are discrete zero‐dimensional molecular complexes. And the adjacent monomeric components are connected by hydrogen bonds to form a supramolecule. Electrochemical properties of the complexes 1 and 2 show that electron transfer of M(II) between M(III) in electrolysis is a quasi‐reversible process.     

Efficient CS Cross‐Coupling of Thiols with Aryl Iodides Catalyzed by Cu(OAc)2·H2O and 2,2′‐Biimidazole

The classical Ullmann C? S cross coupling reaction of aryl iodides with aromatic/alkyl thiols under catalysis of 15 mol% Cu(OAc)₂·H₂O and 15 mol% 2,2′‐biimidazole works at 80°C in DMSO for 3 h to provide a variety of aryl sulfides in good to excellent yields.     

The Interaction of α‐Hydroxycarboxylic Acids with Metal Ions: Lactic Acid (H2L1) and 2‐Methyllactic Acid (H2L2) with Cobalt(II) Crystal and Molecular Structures of [Co(HL1)2(H2O)2]·H2O and [Co(HL2)2(H2O)2]

The cobalt(II) complexes [Co(HL¹)₂(H₂O)₂]·H₂O) ( 1 ) and [Co(HL²)₂(H₂O)₂]( 2 ) [(HL¹)^‐ = (/plusmn;)‐lactate, (HL²)^‐ = 2‐Methyl‐lactate] were prepared and characterized structurally. The cobalt atom is in a distorted octahedral environment in both compounds. Both α‐hydroxycarboxylato ligands are O, O'‐bidentate chelating monoanions. The presence of a lattice water molecule in 1 makes its supramolecular organization different from that of 2 . The thermal behaviour of both compounds was also investigated.     

An Azelaato‐bridged Dinuclear Copper(II) Complex, [Cu2(phen)2(C9H14O4)2] · 6 H2O (phen = 1,10‐phenanthroline)

The title compound [Cu₂(phen)₂(C₉H₁₄O₄)₂] · 6 H₂O was prepared by the reaction of CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen), azelaic acid and Na₂CO₃ in a CH₃OH/H₂O solution. The crystal structure (monoclinic, C2/c (no. 15), a = 22.346(3), b = 11.862(1), c = 17.989(3) Å, β = 91.71(1)°, Z = 4, R = 0.0473, wR² = 0.1344 for 4279 observed reflections) consists of centrosymmetric dinuclear [Cu₂(phen)₂(C₉H₁₄O₄)₂] complexes and hydrogen bonded H₂O molecules. The Cu atom is square‐planar coordinated by the two N atoms of the chelating phen ligand and two O atoms of different bidentate bridging azelaate groups with d(Cu–N) = 2.053, 2.122(2) Å and d(Cu–O) = 1.948(2), 2.031(2) Å. Two azelaate anions bridge two common Cu atoms via the terminal O atoms (d(C–O) = 1.29(2) Å; d(C–C) = 1.550(4)–1.583(4) Å). Phen ligands of adjacent complexes cover each other at distances of about 3.62 Å, indicating π‐π stacking interaction, by which the complexes are linked to 1 D bands.     

Mixed‐ligand Copper(II) Complexes with N‐isopropyl‐iminodiacetato(2‐) and C‐phenyl‐imidazole Ligands. Crystal Structures of H2iPIDA, [Cu(iPIDA)(H2ϕim)(H2O)]·3H2O and [Cu(iPIDA)(H5ϕim)]n

The crystal of the N‐isopropyl‐iminodiacetic acid ( 1 ) consists of a 3D H‐bonded framework where the zwitterion (H₂iPIDA^±) is intra‐stabilized by one N⁺‐H···O interaction and both carboxyl are half‐protonated and involved in linear O‐H···O inter‐molecular bridges of 2.46 Å. The mixed‐ligand complexes [Cu(iPIDA)(H2?im)(H₂O)]·3H₂O ( 2 ) and [Cu(iPIDA)(H5?im)]_n ( 3 ) have also been synthesized and studied by thermal, spectral, magnetic and X‐ray diffraction methods. Both complexes exhibit a square base pyramidal coordination, type 4+1. Compound 3 is the less steric hindered 'remote' isomer, with H5?im instead of H4?im.     

Three New Thioantimonates(V): Solvothermal Syntheses and Crystal Structures of [M(chxn)3]3(SbS4)2·4H2O (M = Ni,Co) and [Co(dien)2][Co(tren)SbS4]2·4H2O

The three new thioantimonates(V) [Ni(chxn)₃]₃(SbS₄)₂·4H₂O ( I ), [Co(chxn)₃]₃(SbS₄)₂·4H₂O ( II ) (chxn is trans‐1,2‐diaminocyclohexane) and [Co(dien)₂][Co(tren)SbS₄]₂·4H₂O ( III ) (dien is diethylenetriamine and tren is tris(2‐aminoethyl)amine) were synthesized under solvothermal conditions. Compounds I and II are isostructural crystallizing in space group C2/c. The structures are composed of isolated [M(chxn)₃]²⁺ complexes (M = Ni, Co), [SbS₄]^3? anions and crystal water molecules. Short S···N/S···O/O···O separations indicate hydrogen bonding interactions between the different constituents. Compound III crystallizes in space group and is composed of [Co(dien)₂]²⁺ and [Co(tren)SbS₄]^? anions and crystal water molecules. In the cationic complex the Co²⁺ ion is in an octahedral environment of two dien ligands whereas in [Co(tren)SbS₄]^? the Co²⁺ ion is in a trigonal bipyramidal coordination of four N atoms of tren and one S atom of the [SbS₄]^3? anion, i.e., two different coordination polyhedra around Co²⁺ coexist in this compound. Like in the former compounds an extended hydrogen bonding network connects the complexes and the water molecules into a three‐dimensional network.     

Electrochemical and Biological Studies on Reactivity of [VO(oda)(H2O)2], [Co(oda)(H2O)2]·H2O,and [Ni(oda)­(H2O)3]·1.5H2O Towards Superoxide Free Radicals

The reactivity of superoxide free radicals (O₂ ^{· –}) generated electrochemically towards the oxydiacetate metal complexes, namely [VO(oda)(H₂O)₂], [Co(oda)(H₂O)₂] · H₂O, and [Ni(oda)(H₂O)₃] · 1.5H₂O (oda = oxydiacetate) was examined by cyclic voltammetry. The measurements were carried out in DMSO solution using a platinum electrode. Based on the height of the anodic peak E_a that corresponds to electrochemical oxidation O₂ ^{· –} → O₂ + e, in the absence and in the presence of the compounds in the mixture, their O₂ ^{· –} scavenge ability was assessed. The influence of the type of the complex was briefly discussed. H₂O₂ was used to induce cellular injury in a mouse hippocampal cell line (HT22). The cytoprotection of chemical compounds was tested at the mitochondrial (MTT test) and plasma membrane level (LDH leakage). Dose‐dependent effect (10 and 100 μM of the complex) of investigated compounds was observed.     

Crystal Structures of [Cu2(bpy)2(H2O)(OH)2(SO4)]·4H2O and [Cu(bpy)(H2O)2]SO4 with bpy = 2, 2′‐Bipyridine

Two sulfato Cu^II complexes [Cu₂(bpy)₂(H₂O)(OH)₂(SO₄)]· 4H₂O ( 1 ) and [Cu(bpy)(H₂O)₂]SO₄ ( 2 ) were synthesized and structurally characterized by single crystal X—ray diffraction. Complex 1 consists of the asymmetric dinuclear [Cu₂(bpy)₂(H₂O)(OH)₂(SO₄)] complex molecules and hydrogen bonded H₂O molecules. Within the dinuclear molecules, the Cu atoms are in square pyramidal geometries, where the equatorial sites are occupied by two N atoms of one bpy ligand and two O atoms of different μ₂—OH groups and the apical position by one aqua ligand or one sulfato group. Through intermolecular O—H···O and C—H···O hydrogen bonds and intermolecular π—π stacking interactions, the dinuclear complex molecules are assembled into layers, between which the hydrogen bonded H₂O molecules are located. The Cu atoms in 2 are octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two H₂O molecules and two sulfato groups with the sulfato O atoms at the trans positions and are bridged by sulfato groups into ¹[Cu(bpy)(H₂O)₂(SO₄)_2/2] chains. Through the interchain π—π stacking interactions and interchain C—H···O hydrogen bonds, the resulting chains are assembled into bi—chains, which are further interlinked into layers by O—H···O hydrogen bonds between adjacent bichains.     

Syntheses and Characterization of Three New Compounds Based on Terephthalate and 2‐(2‐Pyridin‐4‐yl‐vinyl)benzimidazole Ligands

Three new compounds based on H₂BDC and PyBImE [H₂BDC = 1,4‐benzenedicarboxylatic acid, PyBImE = 2‐(2‐pyridin‐4‐yl‐vinyl)benzimidazole], namely, [Co(PyBImE)(BDC)(H₂O)₂] ( 1 ), [Co(PyBImE)₂(HBDC)(BDC)_0.5] ( 2 ), and [(HPyBImE)⁺ · (BDC)²–_0.5 · (H₂BDC)_0.5] ( 3 ), were synthesized by hydrothermal methods and characterized by single‐crystal X‐ray diffraction. Compound 1 is a one‐dimensional chain bridged by terephthalate in a bis(monodentate) fashion. In the complex the nitrogen atom from N_BIm and the coordination water molecule complete the coordination sphere. In complex 2 , the dinuclear cobalt units are bridged by terephthalate in a bis(bidentate) fashion into a one‐dimensional chain, but different from complex 1 , the nitrogen atom from N_Py and the oxygen atom from hydrogenterephthalate complete the coordination sphere. Complex 3 is a co‐crystal with PyBImE and H₂BDC in a 1:1 ratio and the transfer of hydrogen atoms leads the complex into a salt. Interesting supramolecular structures are shown due to the hydrogen bonding as well as π ··· π interactions in the three complexes. Thermal and magnetic properties of 1 and 2 were also studied.