One-dimensional Zigzag Coordination Research Articles

Catena-Poly[[[1-benzoyl-2-(2-hydroxyethyl)-3-(2-pyridyl)guanidine]chloridocopper(II)] chloride 0.61-hydrate

The title copper(II) complex, {[CuCl(C(15)H(16)N(4)O(2))]Cl.0.61H(2)O}(n), is a one-dimensional zigzag coordination polymer structure extending along the (010) direction. The Cu(II) atom has a square-pyramidal geometry, where the basal plane is formed by two cis N atoms and one O atom from the ligand, and by a Cl atom. The apical position is occupied by a carbonyl O atom from a symmetry-related molecule. In the crystal structure, there are O-H...Cl and N-H...Cl hydrogen bonds, which link parallel polymer chains along the c direction, so building a two-dimensional structure via the interstitial Cl atoms.

Assembly of a novel luminescent coordination polymer from europium nitrate and a new semirigid bridging podand

One-dimensional zig-zag coordination polymer has been rationally assembled by the reaction of europium nitrate and a new amide type semirigid bridging podand 1,4-bis{[(2′- m-picolylaminoformyl)phenoxyl]methyl}naphthalene ( L). The coordination chains are further linked by the intermolecular hydrogen bonds to form two-dimensional supramolecular layer structure. At the same time, the luminescent properties of the Eu(III) complex were also investigated. Under the excitation, the complex exhibited characteristic emissions of europium ion.

Unprecedented 3D entanglement of 1D zigzag coordination polymers leading to a robust microporous framework

One-dimensional zigzag coordination chains in four different directions are hierarchically entangled to generate an unprecedented 3D interwoven framework, which exhibits permanent porosity and guest selectivity.

Remarkably Stable Porous Assembly of Nanorods Derived from a Simple Metal−Organic Framework

A new strategy has been described to create a microporous metal−organic framework by assembling nanorodlike constructs equipped with a complementary hydrogen-bonding surface. Guest-accessible channels are located in the internanorod space generated by the self-assembly of the nanorodlike constructs via complementary hydrogen bonding. Thus, reaction of a hydrogen-bond-equipped and conformationally flexible ligand such as N,N‘-bis(3-pyridyl)urea with CuSO4 resulted in the formation of a stable, guest-free microporous MOF wherein a nanorodlike construct is formed that is further self-assembled into a microporous metal−organic framework via self-complementary hydrogen bonding involving a urea backbone and sulfate anion. Because of conformational flexibility, a one-dimensional zigzag coordination polymeric network is also formed. The structures are characterized mainly by single-crystal X-ray diffraction techniques.

One-Dimensional and Two-Dimensional Coordination Polymers from Self-Assembling of Trinuclear Triangular Cu(II) Secondary Building Units

The reactions of pyrazole (Hpz) with some copper(II) carboxylates in the presence of water yield trinuclear copper derivatives characterized by the triangular core [Cu3mu3-OH)(mu-pz)3(RCOO)2] (R = H, C2H5, C3H7). Copper(II) formate gives [Cu3(mu3-OH)(mu-pz)3(HCOO)2(Hpz)2] (1), whereas copper propionate and butyrate afford [Cu3(mu3-OH)(mu-pz)3(C2H5COO)2(EtOH)] (2) and [Cu3(mu3-OH)(mu-pz)3(C3H7COO)2(MeOH)(H2O)] (3), respectively, both containing solvent molecules coordinated to copper atoms. Magnetic susceptibilities are consistent with a single unpaired electron for each trinuclear unit of 1-3, and EPR measurements indicate that higher spin states, generated by exchange coupling between copper atoms, may be populated at room temperature. Density-functional calculations provide the description of the electronic structures of 1-3, allowing, at the same time, the assignment of their UV-vis absorption spectra. X-ray molecular structure determinations show that triangular trinuclear units of 1 are connected to each other through single formate bridges, forming one-dimensional (1D) zigzag coordination polymers, whereas in 2 and 3, two oxygen atoms of two carboxylate ions doubly bridge two copper atoms of different triangles, thus generating hexanuclear units. Moreover, in 2, two other propionate ions link together two hexanuclear units yielding a 12-membered cycle and giving rise to 1D coordination polymers. The supramolecular assemblies of 1-3 are compared to that of the previously reported trinuclear triangular copper(II) derivative [Cu3(mu3-OH)(mu-pz)3(CH3COO)2(Hpz)] (A), where a two-dimensional (2D) coordination polymer is present. The reactions of 3,5-dimethylpyrazole (Hpz) with copper(II) carboxylates in the same conditions yield 1:2 Cu(RCOO)2/Hpz adducts.

A one-dimensional zigzag coordination polymer: {[Ag(2-amino-3-methylpyridine)](ClO4)}∞

The reaction of silver perchlorate with 2-amino-3-methylpyridine gives a one-dimensional zigzag coordination polymer {[Ag(2-amino-3-methylpyridine)](ClO4)}∞ (1) consisting of single chains. The geometry of all Ag(I) cations is linear: each ion links together two 2-pyridyl (Ag1) rings and two 2-amino (Ag2) groups, with the ligand exhibiting a ‘head-to-head’ orientation. Crystal data: monoclinic P2(1)/c, a = 5.2296(8), b = 20.668(3), c = 8.8716(14) Å, β = 100.359(3)°, V = 943.3(3) Å3, Z = 2, D c = 2.214 Mg/m3, μ = 2.409 mm−1, F(000) = 612, R1 = 0.0426, wR1 = 0.0980 [I > 2σ(I)], S = 0.969.

A novel one-dimensional zigzag coordination polymer of copper(II) with dimethylglyoxime

A novel metal-organic based polymeric complex, namely catena-poly­[[bis(μ4-di­methyl­glyoximato)­bis(μ2-di­methyl­gly­oxi­mato)­bis­(di­methyl­glyoxime)­tetracopper(II)] diperchlorate dihydrate], {[Cu4(dmg)2(Hdmg)2(H2dmg)2](ClO4)2·2H2O}∞ (H2dmg is di­methyl­glyoxime, C2H8N2O2), has been synthesized and characterized by single-crystal X-ray diffraction methods. The complex is a one-dimensional zigzag chain coordination polymer, in which the tetranuclear repeat unit is a centrosymmetric Cu4 moiety coordinated to di­methyl­glyoxime ligands only. These units are linked by double Cu—O—Cu bridges in a centrosymmetric rectangular ­junction.

Zn(μ- l)Cl 2] ∞: a one-dimensional (1-D) zigzag coordination chain exhibiting unique two-dimensional (2D) hydrogen-bonding supramolecular architecture

Self-assembly of the versatile bridging ligand 2,5-bis(3-pyridyl)-1,3,4-oxadiazole ( l) with ZnCl 2 in CHCl 3–H 2O medium affords a neutral one-dimensional zigzag coordination polymer [Zn(μ- l)Cl 2] ∞ ( 1), which has been characterized by IR, elemental analyses, thermogravimetric analysis (TGA) and X-ray diffraction techniques. The crystal structure of 1 reveals that the ligand molecules bridge the tetrahedral Zn II centers (ZnN 2Cl 2) in the unprecedented transoid conformation, forming a one-dimensional zigzag coordination chain. The inter-chain C–H···Cl hydrogen bonds between the pyridine rings and the coordinated chloride anions extend these 1-D coordination frameworks to result in a novel 2-D supramolecular architecture, and there exist significant edge-to-edge π–π stacking interactions between the inter-chain neighboring pyridyl rings of the ligand, which may further stabilize this structure.

Varying coordination modes and magnetic properties of copper(II) complexes with diazamesocyclic ligands by altering additional donor pendants on 1,5-diazacyclooctane.

A series of new diazamesocyclic ligands based on a diazamesocycle, 1,5-diazacyclooctane (DACO), functionalized by additional donor groups--1,5-bis(N-1-methylimidazol-2-ylmethyl)-1,5- diazacyclooctane (L1), 1-(2-hydroxybenzyl)-1,5-diazacyclooctane (HL2), 1,5-bis(2-hydroxybenzyl)-1,5-diazacyclooctane (H2L3), and 1-(N-1-methylimidazol-2-ylmethyl)-1,5-diazacyclooctane (L4)--and their Cu(II) complexes have been synthesized and characterized. Single-crystal X-ray diffraction analysis of the four Cu(II) complexes revealed that L1 forms a five-coordinate mononuclear complex, HL2 a N3- mu-bridged binuclear complex, H2L3 an oxygen mu-bridged trinuclear complex, and L4 a one-dimensional zigzag coordination polymeric complex with Cu(II). [CuL1ClO4](ClO4) (I): a = 12.194(2) A, b = 13.351(3) A, c = 14.473(3) A, beta = 107.10(3) degrees, Z = 4. [CuL2(N3)]2 (II): a = 8.1864(6) A, b = 18.141(2) A, c = 9.3307(7) A, beta = 103.662(6) degrees, Z = 2. [Cu3(L3)2Cl2] (III): a = 10.7296(13) A, b = 13.7707(17) A, c = 13.5523(17) A, beta = 106.350(3) degrees, Z = 2. ([CuL4Cl]2ClO4) infinity (IV): a = 7.279(1) A, b = 23.695(5) A, c = 19.308(4) A, beta = 100.28(3) degrees, Z = 8. All four complexes crystallize in the monoclinic crystal system with the P2(1)/c space group, and each Cu(II) center coordinated with DACO is pentacoordinated with a distorted square-pyramidal or trigonal-bipyrimidal coordination environment. In complex IV, the binuclear cation unit [CuL4Cl]2(2+) constitutes the fundamental building block of an infinite alternating zigzag chain structure, and the binuclear unit contains two types of geometries around the Cu(II) centers: the Cu(1) center is a distorted square-pyramidal environment, while the Cu(2) is a distorted trigonal-bipyramidal coordination environment. To the best of our knowledge, this is the first Cu(II) complex of a diazamesocyclic ligand with an infinite polymeric structure. The magnetic properties of complexes II, III, and IV have been investigated by variable-temperature magnetic susceptibility measurements in the solid state. The obtained parameters are 2J = 2.06 cm-1 (II), -345.56 cm-1 (III), and -2.60 cm-1 (IV), which differ greatly from ferromagnetic to weak and strong antiferromagnetic coupling. These results unequivocally indicate that the nature of the pendant arms is a key factor governing the structure and properties of the complexes; therefore, the coordination modes and properties of the metal complexes of a diazamesocycle can be controlled by altering the pendant donors on it. Magneto-structural correlation has been precisely analyzed, and the solution properties of these complexes have also been described.

Self-assembly of a Novel One-dimensional Zigzag Coordination Polymer

Reaction of anhydrous NiBr2 with pyrazine and disodium terephthalate in the presence of water results in the formation of a one-dimensional (1D) coordination polymer [Ni(pyrazine)2(H2O)4] · (terephthalate) 1 which demonstrates a linear zigzag coordination pattern running along the crystallographic c-axis. The title compound crystallizes in the monoclinic space group C2/c with a = 16.833(2), b = 9.173(1), c = 11.107(1) Å, β = 119.373(2)°, and Dc = 1.667 for Z = 4. Final refinement based upon 4345 observed reflections led to a final R value of 0.052 for the polymeric product. The included terephthalate anion participates in eight O—H…O hydrogen bonds to coordinated water molecules.

Thiophene-2,5-dicarboxylic acid incorporated self-assembly of one-, two- and three-dimensional coordination polymers

Six thiophene-2,5-dicarboxylic acid incorporated and self-assembled zinc(II), cobalt(II) and manganese(II) coordination polymers [Zn(Tda)(py)]n (1), [Zn(Tda)(bipy)(H2O)·1.5H2O]n (2), [Zn(Tda)(phen)(H2O)]n (3), [Co(Tda)(phen)(H2O)]n (4), [Mn(Tda)(phen)]n (5) and [Mn(Tda)(H2O)2]n (6) have been synthesised and structurally characterised. Complex 1 is characterised as a two-dimensional parallelogram with a cavity of about 10.4×10.4 A, while complexes 2 and 3 (4) are one-dimensional linear and zig-zag coordination polymers with mainly hydrogen-bonding and stacking interactions contributing to their crystal packing, respectively. Complex 5 is a two-dimensional porous sheet with alternating 16- and 8-membered rings, while complex 6 is a three-dimensional porous coordination polymer. The diverse coordination properties of thiophene-2,5-dicarboxylate make it a good building block for the construction of coordination polymers of different architectures, which are dependent on both the end-capping ligand and the coordination geometry of the metal ions. Physical and thermal properties of these complexes have also been studied.