(4,4′‐Bipyridine)dichloroman­ganese(II), a two‐dimensional ­coordination polymer

The title compound, [MnCl₂(C₁₀H₈N₂)]_n, crystallizes with a two‐dimensional network constructed from linear chains of edge‐sharing MnCl₄ square‐planar units cross‐linked by bidentate 4,4′‐bi­pyridine bridges. The Mn atom and the bipyridine moieties lie on sites with 222 crystallographic symmetry; the Cl atom lies on a twofold axis. The bi­pyridine mol­ecule is twisted about the central C—C bond by 33.5 (3)°.     

Poly­[[[aqua­manganese(II)]‐μ2‐4,4′‐bi­pyridine‐μ3‐succinato] 4,4′‐bi­pyridine hemisolvate]

The polymeric title complex, {[Mn(C₄H₄O₄)(C₁₀H₈N₂)(H₂O)]·0.5C₁₀H₈N₂}_n, possesses a three‐dimensional open‐framework structure, with the solvate 4,4′‐bi­pyridine (bipy) mol­ecules, which lie around centers of inversion, clathrated in the channels of the framework. The Mn^II center is surrounded by three succinate (succ) ligands, one water mol­ecule and two bipy ligands, and displays a slightly distorted octahedral coordination environment, with cis angles ranging from 84.14 (12) to 96.56 (11)°. Each succ dianion coordinates to three Mn^II atoms, thus acting as a bridging tridentate ligand; in turn, the Mn^II atoms are bridged by three succ ligands, thus forming a two‐dimensional Mn–succ sheet pillared by the bridging bipy ligands. Two hydrogen‐bonding interactions, involving the water mol­ecules and the carboxy O atoms of the succ ligands, are present in the crystal structure.     

A two‐dimensional manganese(II) coordination polymer: poly­[[di­aqua­manganese(II)]‐μ‐4,4‐bi­pyridine‐κ2N:N′‐μ‐(p‐phenyl­ene­dioxy­diacetato)‐κ2O:O′]

In the title two‐dimensional coordination polymer, [Mn(1,4‐BDOA)(4,4‐bipy)(H₂O)₂]_n [1,4‐BDOA²⁻ is the p‐phenyl­ene­dioxy­di­acetate dianion (C₁₀H₈O₆) and 4,4‐bipy is 4,4‐bi­pyridine (C₁₀H₈N₂)], each Mn^II atom displays octahedral coordination by two O atoms of the 1,4‐BDOA²⁻ groups, two N atoms of the 4,4‐bipy ligands and two solvent water mol­ecules. The Mn^II atom, 4,4‐bipy ligand and 1,4‐BDOA²⁻ group occupy different inversion centres. Adjacent Mn^II atoms are bridged by 1,4‐BDOA²⁻ groups and 4,4‐bipy ligands, forming a two‐dimensional network with Mn⋯Mn separations of 11.592 (2) and 11.699 (2) Å. Hydro­gen bonds from a water O—H group link the layers in the third dimension.     

The supramolecular architecture in 4,4′‐bipyridinium bis(hydrogen oxalate)

The asymmetric unit of the title compound, C₁₀H₁₀N₂²⁺·2C₂HO₄⁻, consists of one half of a 4,4′‐bipyridinium cation, which has inversion symmetry, and a hydrogen oxalate anion, in which an intramolecular hydrogen bond exists. The cations and anions are connected by O—H...O, N—H...O and C—H...O hydrogen bonds, forming a two‐dimensional network, whereas π–π stacking interactions involving the 4,4′‐bipyridinium cations lead to the formation of a three‐dimensional supramolecular structure. An unusual deca‐atomic ring is formed between two hydrogen oxalate anions, which are linked side‐to‐side via O—H...O hydrogen‐bonding interactions.     

catena‐Poly[[[tetra­aqua­zinc(II)]‐μ‐4,4′‐bipyridine] bis­(4‐hydroxy­benzene­sulfonate) trihydrate]

In the title compound, {[Zn(C₁₀H₈N₂)(H₂O)₄](C₆H₅O₄S)₂·3H₂O}_n, the Zn atom, the bipyridine ligand and one of water mol­ecules are located on twofold rotation axes. The Zn atom is coordinated by four O atoms from four water mol­ecules and two N atoms from two 4,4′‐bipyridine mol­ecules in a distorted octa­hedral geometry. The Zn²⁺ ions are linked by the 4,4′‐bipyridine mol­ecules to form a one‐dimensional straight chain propagating along the c axis. The 4‐hydroxy­benzene­sulfonate counter‐ions are bridged by the solvent water mol­ecules through hydrogen bonds to generate a two‐dimensional layer featuring large pores. In the crystal packing, the intra­layer pores form one‐dimensional channels along the c axis, in which the one‐dimensional [Zn(C₁₀H₈N₂)(H₂O)₄]²⁺ chains are encapsulated. Electrostatic inter­actions between cations and anions and extensive hydrogen bonds result in a three‐dimensional supra­molecular structure.     

4,4′‐Thio­dipyridinium tetra­chloro­copper(II)

The title compound, (C₁₀H₁₀N₂S)[CuCl₄], was obtained by the reaction of cupric chloride with pyridine‐4‐thiol in a mixture of aceto­nitrile and tetra­hydro­furan, suggesting that the desulfurization and coupling reactions of pyridine‐4‐thiol occurred in the presence of the Cu²⁺ ion. X‐ray diffraction analysis reveals the presence of one 4,4′‐thio­dipyridinium cation, H₂bps²⁺, and one [CuCl₄]²⁻ anion. The cations interact with the anions via N—H⋯Cl hydrogen‐bonding interactions to form a closed `chair' conformation.     

Poly[[[aqua­(2,2′‐bipyridine‐κ2N,N′)manganese(II)]‐μ3‐acetyl­enedicarboxylato‐κ3O:O′:O′′] monohydrate]

In the title complex, {[Mn(C₄O₄)(C₁₀H₈N₂)(H₂O)]·H₂O}_n, each Mn^II ion has a distorted octa­hedral coordination formed by two N atoms of a 2,2′‐bipyridine ligand, three carboxyl O atoms of three different acetyl­ene­dicarboxyl­ate ligands and one coordinated water mol­ecule. The acetyl­ene­dicarboxyl­ate ligands act in a tridentate mode connecting adjacent Mn^II ions and constructing a two‐dimensional structure which can be regarded as an unusual plywood‐like stacked network.     

[2,5‐Bis(2,2′‐bipyridyl‐6‐yl)‐3,4‐diazahexa‐2,4‐diene]dichloridomanganese(II): from a mononuclear compound to a three‐dimensional supramolecular framework through C—H...Cl hydrogen bonds and π–π stacking interactions

The title compound, [MnCl₂(C₂₄H₂₀N₆)], has been synthesized and characterized based on the multifunctional ligand 2,5‐bis(2,2′‐bipyridyl‐6‐yl)‐3,4‐diazahexa‐2,4‐diene (L). The Mn^II centre is five‐coordinate with an approximately square‐pyramidal geometry. The L ligand acts as a tridendate chelating ligand. The mononuclear molecules are bridged into a one‐dimensional chain by two C—H...Cl hydrogen bonds. These chains are assembled into a two‐dimensional layer through π–π stacking interactions between adjacent uncoordinated bipyridyl groups. Furthermore, a three‐dimensional supramolecular framework is attained through π–π stacking interactions between adjacent coordinated bipyridyl groups.     

catena‐Poly[[chloro­dipyridine­manganese(II)]‐μ3‐6‐oxo‐1,6‐dihydro­pyridine‐2‐carboxyl­ato]

The title one‐dimensional chain polymer complex, [Mn(C₆H₄NO₃)Cl(C₆H₅N)₂]_n, was isolated from the reaction of MnCl₂ with 6‐oxo‐1,6‐dihydro­pyridine‐2‐carboxylic acid (HpicOH) in pyridine. The asymmetric unit contains one [Mn(HPicO)Cl(py)₂] moiety (py is pyridine), with the (HpicO)⁻ ligand acting in a tridentate manner via the two carboxyl­ate O atoms and the pyridone O atom. The operation of inversion centres generates eight‐ and 14‐membered rings and, in conjunction with an a‐axis translation, leads to an infinite chain extending along [100]. The Mn⋯Mn separations in this chain are 5.1069 (6) and 7.1869 (6) Å. The Mn^II atom has a distorted octahedral coordination, with trans‐axial pyridine ligands and with three O atoms and the Cl atom in the equatorial plane. The conformation of the 14‐membered ring is stabilized by pairs of inversion‐related N—H⋯O hydrogen bonds.     

Di­aqua(2,2′‐bi­pyridine)­malonato­manganese(II)

In the crystal structure of the title compound, [Mn(C₃H₂O₄)(C₁₀H₈N₂)(H₂O)₂], the Mn^II atom demonstrates a distorted octahedral geometry, being coordinated by two N atoms of a 2,2′‐bi­pyridine ligand, two O atoms from the carboxyl­ate groups of the chelating malonate dianion and two O atoms of two cis water mol­ecules. The complex mol­ecules are linked to form a three‐dimensional supramolecular array by both hydrogen‐bonding interactions between coordinated water and the carboxyl­ate groups of neighboring mol­ecules and aromatic π–π‐stacking interactions of the bi­pyridine rings.     

Poly[diaqua­(μ‐4,4′‐bipyridine)tetra­kis­(μ‐ferro­cenecarboxyl­ato)bis­(ferro­cenecarboxyl­ato)­tri­man­ganese(II)]

The title compound, [Mn₃Fe₆(C₅H₅)₆(C₆H₄O₂)₆(C₁₀H₈N₂)(H₂O)₂]_n, consists of two crystallographically unique Mn^II centers. One is situated on an inversion center and is octa­hedrally coordinated by two N atoms from two bridging 4,4′‐bipyridine (4,4′‐bipy) ligands and four O atoms, two from different bridging ferrocenecarboxyl­ate (μ₂‐FcCOO⁻; Fc is ferrocene) units and two from aqua ligands. The two halves of each 4,4′‐bipy ligand are related by a center of symmetry. The second Mn^II center is in a strongly distorted tetra­gonal–pyramidal geometry, coordinated by five O atoms, three from three μ₂‐FcCOO⁻ units and two from a fourth, chelating, η²‐FcCOO⁻ unit. The FcCOO⁻ units function as bridging ligands to adjacent Mn^II centers, leading to the formation of linear ⋯Mn1Mn2Mn2Mn1⋯ chains. Adjacent chains are further bridged by 4,4′‐bipy ligands, resulting in a two‐dimensional layered polymer.     

A novel one‐dimensional complex: catena‐poly­[[manganese(III)‐di‐μ‐2‐[(2‐hydroxy­ethyl)­imino­methyl]­phenolato‐κ2O1,N:κO2;κO2:κ2O1] chloride]

In the title one‐dimensional complex, {[Mn^III(C₉H₁₀NO₂)₂]Cl}_n, the Schiff base ligand 2‐[(2‐hydroxy­ethyl)­imino­methyl]­phenolate (Hsae⁻) functions as both a bridging and a chelating ligand. The Mn^III ion is six‐coordinated by two N and four O atoms from four different Hsae⁻ ligands, yielding a distorted MnO₄N₂ octahedral environment. Each [Mn^III(Hsae)₂]⁺ cationic unit has the Mn atom on an inversion centre and each [Mn^III(Hsae)₂]⁺ cation lies about another inversion centre. The chain‐like complex is further extended into a three‐dimensional network structure through Cl⋯H—O hydrogen bonds and C—H⋯π contacts involving the Hsae⁻ rings.     

catena‐Poly[[(2,2′‐biimidazole‐κ2N,N′)chloro­copper(II)]‐μ‐chloro]

In the polymeric title compound, [CuCl₂(C₆H₆N₄)]_n, each Cu^II ion is five‐coordinated by four basal atoms (two N atoms from a 2,2′‐biimidazole mol­ecule and two Cl⁻ anions) and one axial Cl⁻ anion, in a distorted square‐pyramidal coordination geometry. Cl⁻ anions bridge the {Cu(C₆H₆N₄)Cl} units into one‐dimensional linear chains, which are reinforced by π–π inter­actions. Adjacent linear chains are linked by N—H⋯Cl hydrogen bonds, resulting in a grid layer. The hydrogen‐bonding pattern can be described in graph‐set notation as C(9)R(9)R(14). This study extends our knowledge of the multifunctional properties of the 2,2′‐biimidazole ligand and of the coordination stereochemistry of copper(II).     

catena‐Poly[[(1,10‐phenanthroline‐κ2N,N′)manganese(II)]‐di‐μ‐salicylato‐κ4O:O′]

In the title polymeric complex, [Mn(C₇H₅O₃)₂(C₁₂H₈N₂)]_n, the Mn^II atom is located on a twofold axis and displays a distorted octa­hedral coordination geometry, formed by four salicylate anions and one 1,10‐phenanthroline (phen) mol­ecule. The salicylate anions doubly bridge the Mn^II atoms to form one‐dimensional polymeric chains. A comparison of Mn—O bond distances with the corresponding Mn—O—C angles suggests a significant electrostatic content in the Mn—O bonds. A face‐to‐face distance of 3.352 (7) Å between neighbouring parallel phen planes indicates π–π stacking inter­actions between polymeric chains.     

Poly­[[di­aqua­cobalt(II)]‐μ‐4,4′‐bi­pyridine‐κ2N:N′‐μ‐p‐phenyl­enebis­(oxy­acetato)‐κ2O:O′]

The title compound, [Co^II(C₁₀H₈O₆)(C₁₀H₈N₂)(H₂O)₂]_n, was obtained by the hydro­thermal reaction of CoSO₄ with benzene‐1,4‐dioxy­di­acetate [systematic name: p‐phenyl­ene­bis­(oxy­acetate)] and 4,4′‐bi­pyridine (4,4′‐bpy). The Co atom lies at an inversion center and the benzene‐1,4‐dioxydiacetate and 4,4′‐bipyridine moieties lie about other inversion centers. The benzene‐1,4‐dioxydiacetate ligands bridge the octahedral Co^II coordination centers, forming a one‐dimensional zigzag chain. The chains are further bridged by 4,4′‐bpy ligands, forming a novel two‐dimensional supramolecular architecture. Hydro­gen‐bonding interactions between the coordinated water mol­ecules and the carboxyl­ate O atoms lead to the formation of a three‐dimensional network structure.     

Hydro­gen‐bonded supramolecular motifs in 4,4′‐bipyridinium 8‐hydroxy‐7‐iodo­quinoline‐5‐sulfonate dihydrate

In the title compound, C₁₀H₉N₂⁺·C₉H₅INO₄S⁻·2H₂O, the 4,4′‐bi­pyridine mol­ecule is protonated at one of the pyridine N atoms. These moieties self‐assemble into a supramolecular chain along the a axis through N—H⋯N hydrogen bonds. The quinolinol OH group acts as a donor with respect to a sulfonate O atom [O—H⋯O(sulfonate)] and acts as an acceptor with respect to a C—H group of ferron [C—H⋯O(hydroxy)], forming a supramolecular chain along the b axis. These two types of supramolecular chains (one type made up of bi­pyridine motifs and the other made up of sulfoxine motifs) interact viaπ–π stacking, generating a three‐dimensional framework. These chains are further crosslinked by C—­H⋯O hydrogen bonds and O—H⋯O hydrogen bonds involving water mol­ecules.     

catena‐Poly­[[aqua(2,2′‐bi­pyridine‐κ2N,N′)­manganese(II)]‐μ‐terephthalato‐κ3O,O′:O′′]

The title complex, [Mn(C₈H₄O₄)(C₁₀H₈N₂)(H₂O)]_n, takes the form of a zigzag chain, with the terephthalate dianion (tp) acting as a tridentate ligand. The Mn^II center is surrounded by two tp ligands, one water mol­ecule and one 2,2′‐bi­pyridine (bipy) ligand and exhibits a severely distorted octahedral coordination environment, with cis angles ranging from 57.31 (8) to 123.97 (11)°. The complete solid‐state structure can be described as a three‐dimensional supramolecular framework stabilized by hydrogen‐bonding interactions involving the coordinated water mol­ecule and the carboxy O atoms of the tp ligands, and by π–π stacking interactions involving the bipy rings and the benzene ring of the tp ligand.     

A novel cadmium(II) coordination polymer with biphenyl‐3,3′,4,4′‐tetra­carboxylic acid and 4,4′‐bipyridine

A novel cadmium(II) coordination polymer, poly[[[bis­(4,4′‐bipyridine)cadmium(II)]‐μ₃‐4,4′‐dicarboxy­biphenyl‐3,3′‐di­carboxyl­ato] 0.35‐hydrate], {[Cd(C₁₆H₈O₈)(C₁₀H₈N₂)₂]·0.35H₂O}_n, was obtained by reaction of Cd(CH₃COO)₂·3H₂O, 4,4′‐bipyridine (4,4′‐bpy) and biphenyl‐3,3′,4,4′‐tetra­car­boxylic acid (H₄L) under hydro­thermal conditions. Each Cd^II atom lies at the centre of a distorted octa­hedron, coordinated by four O atoms from three H₂L²⁻ ligands and N atoms from two monodentate 4,4′‐bpy ligands. Each H₂L²⁻ ligand coordinates to three Cd^II atoms through two carboxyl­ate groups, one acting as a bridging bidentate ligand and the other in a chelating bidentate fashion. Two Cd atoms, two H₂L²⁻ anions and four 4,4′‐bpy ligands form a ring dimer node, which links into an extended broad zonal one‐dimensional chain along the c axis.     

catena‐Poly[[[triaqua­sulfato­cobalt(II)]‐μ‐4,4′‐bipyridine] ethane‐1,2‐diol solvate]

In the title compound, {[Co(SO₄)(C₁₀H₈N₂)(H₂O)₃]·C₂H₆O₂}_n, each Co^II center is octa­hedrally coordinated by two N atoms from two bridging 4,4′‐bipyridine (bipy) ligands and four O atoms, one from a monodentate sulfate ligand and three from aqua ligands. The bipy ligands occupy special positions of site symmetry and bridge adjacent cobalt(II) centers to form one‐dimensional linear coordination chains. Adjacent chains are arranged in a cross‐like fashion around the mid‐point of the bipy ligands, resulting in a three‐dimensional supra­molecular array.     

catena‐Poly[[[cis‐aqua­bis(4‐carboxy­cyclo­hexane‐1‐carboxyl­ato‐κ2O,O′)cadmium(II)]‐μ‐4,4′‐bipyridine‐κ2N:N] monohydrate]

The title complex, {[Cd(C₈H₁₁O₄)₂(C₁₀H₈N₂)(H₂O)]·H₂O}_n, consists of linear chains formed through 4,4′‐bipyridine ligands linking seven‐coordinated Cd^II ions. Each Cd^II ion is in a distorted penta­gonal–bipyramidal environment, coordinated by one water ligand, two 4‐carboxy­cyclo­hexane‐1‐carboxyl­ate ligands and one bridging 4,4′‐bipyridine ligand to generate linear chains. The water mol­ecules and the Cd atom on one side, and the 4,4′‐bipyridine unit on the other, are bisected by two sets of twofold axes. The carboxylate group of the 4‐carboxy­cyclo­hexane‐1‐carboxyl ligand chelates a Cd^II ion, while the (protonated) carboxyl group forms hydrogen bonds with adjacent chains, resulting in a layered structure. This is the first reported occurrence of a dicarboxycyclo­hexane ligand exhibiting a non‐bridging coordination mode.