A two‐dimensional CdII coordination polymer with 2,2′‐(disulfanediyl)dibenzoate and 1,10‐phenanthroline ligands

In poly[[μ₃‐2,2′‐(disulfanediyl)dibenzoato‐κ⁵O:O,O′:O′′,O′′′](1,10‐phenanthroline‐κ²N,N′)cadmium(II)], [Cd(C₁₄H₈O₄S₂)(C₁₂H₈N₂)]_n, the asymmetric unit contains one Cd^II cation, one 2,2′‐(disulfanediyl)dibenzoate anion (denoted dtdb²⁻) and one 1,10‐phenanthroline ligand (denoted phen). Each Cd^II centre is seven‐coordinated by five O atoms of bridging/chelating carboxylate groups from three dtdb²⁻ ligands and by two N atoms from one phen ligand, forming a distorted pentagonal–bipyramidal geometry. The Cd^II cations are bridged by dtdb²⁻ anions to give a two‐dimensional (4,4) layer. The layers are stacked to generate a three‐dimensional supramolecular architecture via a combination of aromatic C—H...π and π–π interactions. The thermogravimetric and luminescence properties of this compound were also investigated.     

A novel one‐dimensional zinc coordination polymer containing 4‐methylbenzoate and 4,4‐bipyridine

The title compound, catena‐poly[[tris(μ‐4‐methylbenzoato)‐κ²O:O;κ⁴O:O′‐(4‐methylbenzoato‐κ²O,O′)dizinc(II)]‐μ‐4,4′‐bipyridine‐κ²N:N′], [Zn₂(C₈H₇O₂)₄(C₁₀H₈N₂)]_n, is a novel coordination polymer. The asymmetric unit contains two unique Zn^II ions, four 4‐methylbenzoate ligands and one 4,4′‐bipyridine (4,4′‐bpy) ligand, all in general positions. The four 4‐methylbenzoate ligands link the two Zn^II centres to form a dinuclear unit, with a Zn...Zn separation of 3.188 (2) Å, which can be regarded as a supramolecular secondary building unit (SBU). These SBUs are further bridged by 4,4′‐bpy ligands, forming a novel one‐dimensional infinite chain. There are π–π stacking interactions between the benzene rings of the 4‐methylbenzoate ligands and the pyridyl rings of the 4,4′‐bpy ligands, leading to the formation of a corrugated layer. These layers are further assembled via C—H...O hydrogen bonds into a three‐dimensional supramolecular network structure. Coordination polymers such as the title compound are of interest for their potential applications as functional materials.     

A one‐dimensional CdII coordination polymer constructed from 4‐(dimethylamino)pyridinium‐1‐acetate ligands and thiocyanate coordination bridges

A new cadmium–thiocyanate complex, namely catena‐poly[1‐carboxymethyl‐4‐(dimethylamino)pyridinium [cadmium(II)‐tri‐μ‐thiocyanato‐κ⁴N:S;κ²S:N] [[[4‐(dimethylamino)pyridinium‐1‐acetate‐κ²O,O′]cadmium(II)]‐di‐μ‐thiocyanato‐κ²N:S;κ²S:N]], {(C₉H₁₃N₂O₂)[Cd(NCS)₃][Cd(NCS)₂(C₉H₁₂N₂O₂)]}_n, was synthesized by the reaction of 4‐(dimethylamino)pyridinium‐1‐acetate, cadmium nitrate tetrahydrate and potassium thiocyanide in aqueous solution. In the crystal structure, two types of Cd^II atoms are observed in distorted octahedral coordination environments. One type of Cd^II atom is coordinated by two O atoms from the carboxylate group of the 4‐(dimethylamino)pyridinium‐1‐acetate ligand and by two N atoms and two S atoms from four different thiocyanate ligands, while the second type of Cd^II atom is coordinated by three N atoms and three S atoms from six different thiocyanate ligands. Neighbouring Cd^II atoms are linked by thiocyanate bridges to form a one‐dimensional zigzag chain and a one‐dimensional coordination polymer. Hydrogen‐bond interactions are involved in the formation of the supramolecular network.     

A coordination polymer consisting of two different one‐dimensional copper(II) chains

The title compound, catena‐poly[[[diaqua(methanol‐κO)copper(II)]‐μ‐N‐(4‐methylpyrimidin‐2‐yl‐κN¹)pyrazin‐2‐amine‐κ²N¹:N⁴] [[aqua(aqua/methanol‐κO)(perchlorato‐κO)copper(II)]‐μ‐N‐(4‐methylpyrimidin‐2‐yl‐κN¹)pyrazin‐2‐amine‐κ²N¹:N⁴] tris(perchlorate) methanol monosolvate 1.419‐hydrate], {[Cu(C₉H₉N₅)(CH₃OH)(H₂O)₂][Cu(C₉H₉N₅)(ClO₄)(CH₃OH)_0.581(H₂O)_1.419](ClO₄)₃·CH₃OH·1.419H₂O}_n, is a one‐dimensional straight‐chain polymer of N‐(4‐methylpyrimidin‐2‐yl)pyrazin‐2‐amine (L) with Cu(ClO₄)₂. The complex consists of two crystallographically independent one‐dimensional chains in which the Cu^II atoms exhibit two different octahedral coordination geometries. The L ligand coordinates to two Cu^II centres in a tridentate manner, with the pyrazine ring acting as a bridge linking the Cu^II coordination units and building an infinite one‐dimensional chain. Extensive hydrogen bonding among perchlorate anions, water molecules and L ligands results in three‐dimensional networks.     

A novel nickel(II) coordination polymer incorporating 1,4‐phenylene­diacetic acid and 1,10‐phenanthroline

The title nickel(II) coordination polymer, viz. poly[[bis­(1,10‐phenanthroline)tris­(μ₃‐1,4‐phenyl­enediacetato)trinickel(II)] dihydrate], {[Ni₃(C₁₀H₈O₄)₃(C₁₂H₈N₂)₂]·2H₂O}_n, consists of linear trinuclear building blocks with two crystallographically unique Ni atoms. One Ni^II atom and the geometric centre of one 1,4‐phenyl­enediacetate ligand in the trinuclear unit both lie on inversion centres, while the other unique Ni^II atom lies near the inversion centre, together with another 1,4‐phenyl­enediacetate ligand. Each pair of adjacent trinuclear units is bridged by 1,4‐phenyl­enediacetate ligands, forming two kinds of infinite chains along the a and b axes, respectively. These two kinds of chains crosslink to yield a two‐dimensional network in the ab plane. The two‐dimensional sheets further stack along the c axis viaπ–π stacking inter­actions and hydrogen bonds, forming a three‐dimensional supramolecular structure.     

A one‐dimensional coordination polymer with a three‐dimensional supramolecular framework: catena‐poly[[[(3,4,7,8‐tetramethyl‐1,10‐phenanthroline)cadmium(II)]‐μ3‐4,4′‐sulfonyldibenzoato] trihydrate]

In the title mixed‐ligand metal–organic polymeric compound, {[Cd(C₁₄H₈O₆S)(C₁₆H₁₆N₂)]·3H₂O}_n, the asymmetric unit contains a crystallographically unique Cd^II atom, one doubly deprotonated 4,4′‐sulfonyldibenzoic acid (H₂SDBA) ligand, one 3,4,7,8‐tetramethyl‐1,10‐phenanthroline (TMPHEN) molecule and three solvent water molecules. Each Cd^II centre is six‐coordinated by two O atoms from a chelating carboxylate group of a SDBA²⁻ ligand, two O atoms from monodentate carboxylate groups of two different SDBA²⁻ ligands and two N atoms from a chelating TMPHEN ligand. There are two coordination patterns for the carboxylate groups of the SDBA²⁻ ligand, with one in a μ₁‐η¹:η¹ chelating mode and the other in a μ₂‐η¹:η¹ bis‐monodentate mode. Single‐crystal X‐ray diffraction analysis revealed that the title compound is a one‐dimensional double‐chain polymer containing 28‐membered rings based on the [Cd₂(CO₂)₂] rhomboid subunit. More interestingly, a chair‐shaped water hexamer cluster is observed in the compound.     

A one‐dimensional mixed‐anion lead(II) coordination polymer: catena‐poly[[(1,10‐phenanthroline)lead(II)]‐μ‐benzoato‐μ‐nitrato‐[(1,10‐phenanthroline)lead(II)]‐di‐μ‐benzoato]

In the title polymeric compound, [Pb₂(C₇H₅O₂)₃(NO₃)(C₁₂H₈N₂)₂]_n, both independent Pb atoms adopt an eight‐coordinate geometry formed by one nitrate, three benzoate and one 1,10‐phenanthroline ligand. The one‐dimensional polymer consists of dimeric [Pb₂(C₇H₅O₂)₃(NO₃)(C₁₂H₈N₂)₂] units, in which all nitrate and benzoate ligands act in a bridging–chelating coordination mode.     

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.     

A novel cadmium(II) coordination polymer containing two kinds of independent one‐dimensional chain

The structure of the title compound, catena‐poly[[cadmium(II)‐di‐μ‐chlorido‐μ‐(1,4‐diazoniabicyclo[2.2.2]octane‐1‐carboxylato)] [[aquachloridocadmium(II)]‐di‐μ‐chlorido] dihydrate], {[Cd(C₈H₁₅N₂O₂)Cl₂][CdCl₃(H₂O)]·2H₂O}_n, contains two kinds of independent one‐dimensional chain, viz. {[Cd(C₈H₁₅N₂O₂)Cl₂]⁺}_n and {[CdCl₃(H₂O)]⁻}_n, and uncoordinated water molecules. Each Cd^II cation in the {[Cd(C₈H₁₅N₂O₂)Cl₂]⁺}_n chain is octahedrally coordinated by two pairs of bridging chloride ligands and two O atoms from different bridging carboxylate groups. Cd^II cations in the {[CdCl₃(H₂O)]⁻}_n chain are also octahedrally surrounded by four bridging chloride ligands, one terminal chloride ligand and one coordinated water molecule. Hydrogen bonds between solvent water molecules and these two independent chains generate a three‐dimensional framework containing two‐dimensional zigzag layers.<!?tpb=18pt>     

A one‐dimensional zinc(II) coordination polymer based on mixed multidentate N‐ and O‐donor ligands

In the title coordination polymer, catena‐poly[[bis[{1‐[(1H‐benzimidazol‐2‐yl‐κN³)methyl]‐1H‐tetrazole}zinc(II)]‐bis(μ₄‐pentane‐1,5‐dioato‐1:2:1′:2′κ⁴O¹:O^1′:O⁵:O^5′)] methanol disolvate], {[Zn(C₅H₆O₄)(C₉H₈N₆)]·CH₃OH}_n, each Zn^II ion is five‐coordinated by four O atoms from four glutarate ligands and by one N atom from a 1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole (bimt) ligand, leading to a slightly distorted square‐pyramidal coordination environment. Two Zn^II ions are linked by four bridging glutarate carboxylate groups to generate a dinuclear [Zn₂(CO₂)₄] paddle‐wheel unit. The dinuclear units are further connected into a one‐dimensional chain via the glutarate ligands. The bimt ligands coordinate to the Zn^II ions in a monodentate mode and are pendant on both sides of the main chain. In the crystal, the chains are linked by O—H...O and N—H...O hydrogen bonds into a two‐dimensional layered structure. Adjacent layers are further packed into a three‐dimensional network through van der Waals forces. A thermogravimetric analysis was carried out and the photoluminescent behaviour of the polymer was investigated.     

Two‐dimensional ZnII and one‐dimensional CoII coordination polymers based on benzene‐1,4‐dicarboxylate and pyridine ligands

Coordination polymers constructed from metal ions and organic ligands have attracted considerable attention owing to their diverse structural topologies and potential applications. Ligands containing carboxylate groups are among the most extensively studied because of their versatile coordination modes. Reactions of benzene‐1,4‐dicarboxylic acid (H₂BDC) and pyridine (py) with Zn^II or Co^II yielded two new coordination polymers, namely, poly[(μ₄‐benzene‐1,4‐dicarboxylato‐κ⁴O:O′:O′′:O′′′)(pyridine‐κN)zinc(II)], [Zn(C₈H₄O₂)(C₅H₅N)]_n, (I), and catena‐poly[aqua(μ₃‐benzene‐1,4‐dicarboxylato‐κ³O:O′:O′′)bis(pyridine‐κN)cobalt(II)], [Co(C₈H₄O₂)(C₅H₅N)₂(H₂O)]_n, (II). In compound (I), the Zn^II cation is five‐coordinated by four carboxylate O atoms from four BDC²⁻ ligands and one pyridine N atom in a distorted square‐pyramidal coordination geometry. Four carboxylate groups bridge two Zn^II ions to form centrosymmetric paddle‐wheel‐like Zn₂(μ₂‐COO)₄ units, which are linked by the benzene rings of the BDC²⁻ ligands to generate a two‐dimensional layered structure. The two‐dimensional layer is extended into a three‐dimensional supramolecular structure with the help of π–π stacking interactions between the aromatic rings. Compound (II) has a one‐dimensional double‐chain structure based on Co₂(μ₂‐COO)₂ units. The Co^II cations are bridged by BDC²⁻ ligands and are octahedrally coordinated by three carboxylate O atoms from three BDC²⁻ ligands, one water O atom and two pyridine N atoms. Interchain O—H…O hydrogen‐bonding interactions link these chains to form a three‐dimensional supramolecular architecture.     

A novel copper(II) complex with 1,10‐phenanthroline and ciprofloxacin

The X‐ray structure analysis of the title compound, chloro[1‐cyclopropyl‐6‐fluoro‐1,4‐dihydro‐4‐oxo‐7‐(piperazin‐4‐ium‐1‐yl)‐3‐quinolinecarboxylate‐κ²O³,O⁴](1,10‐phenanthroline‐κ²N,N′)copper chloride dihydrate, [CuCl(C₁₇H₁₈FN₃O₃)(C₁₂H₈N₂)]Cl·2H₂O or [CuCl(cfH)(phen)]Cl·2H₂O, where cfH is 1‐cyclopropyl‐6‐fluoro‐1,4‐dihydro‐4‐oxo‐7‐(piperazin‐4‐ium‐1‐yl)‐3‐quinolinecarboxylate and phen is 1,10‐phenanthroline, shows that the geometry around the Cu ion is a slightly distorted square pyramid. Two O atoms of the carbonyl and carboxyl groups of ciprofloxacin and two N atoms of 1,10‐phenanthroline are coordinated to the metal centre in the equatorial plane, and a Cl⁻ ion is coordinated at the apical position. Extensive intermolecular hydrogen bonding produces a supramolecular structure that consists of alternating six‐ and 12‐membered rings.     

A novel one‐dimensional coordination polymer with Cd2+ and diethylenetriaminepentaacetic acid

catena‐Poly­[[[bis­[di­aqua(4,4′‐bi­pyridine)­cadmium(II)]‐bis­[μ‐(N′′‐carboxy­methyl­diethyl­enetri­amine‐N,N,N′,N′′‐tetra­ace­ta­to)­cadmium(II)]]‐μ‐4,4′‐bi­pyridine] tetradecahydrate], [Cd₄­(C₁₄H₁₉N₃O₁₀)₂(C₁₀H₈N₂)₃(H₂O)₄]·14H₂O or [Cd₄(HD­TPA)₂(BPY)₃(H₂O)₄]·14H₂O, where BPY is 4,4′‐bi­pyridine and HDTPA^4? is N′′‐carboxy­methyl­diethyl­enetri­amine‐N,N,N′,N′′‐tetra­acetate, consists of a one‐dimensional coordination polymer formed from a secondary building unit which comprises four Cd centres. The chain structure of the title compound was obtained by the use of a multidentate organic ligand, N,N,N′,N′′,N′′‐diethyl­enetri­amine­penta­acetic acid (H₅DTPA), which forms multiple chelate rings with the Cd metal centres. An extended network is formed via hydrogen bonds.     

catena‐Poly­[[dicyan­amido(1,10‐phen­anthroline)copper(II)]‐μ‐dicyan­amido]

The title compound, [Cu(C₂N₃)₂(C₁₂H₈N₂)]_n, has a sheet‐like structure, built by [Cu(phen)(dca)₂]_n (phen is 1,10‐phenanthroline and dca is dicyan­amide) chains which are interconnected by secondary long Cu—N bonds between the chains. The Cu²⁺ ion is in a distorted tetragonal bipyramidal (5 + 1) coordination environment. The sheets stack into the three‐dimensional crystal structure through aromatic interactions between the coordinated phen ligands of adjacent sheets.     

Crystallographic report: Crystal structure of a one‐dimensional zinc(II) coordination polymer containing 4,4′‐biphenyldicarboxylate hemihydrate

A one‐dimensional zinc(II) coordination polymer has been constructed from zinc(II), 4,4′‐biphenyldicarboxylate and pyridine in which each zinc(II) atom is coordinated by two pyridine ligands and two monodentate 4,4′‐biphenyldicarboxylate ligands that define a distorted tetrahedral geometry. Copyright © 2003 John Wiley & Sons, Ltd.     

A one‐dimensional manganese(III)–porphyrin coordination polymer: crystal structure and photophysical properties

A novel manganese(III)–porphyrin complex, namely, catena‐poly[[chloridomanganese(III)]‐μ₂‐5,10,15,20‐tetrakis(pyridin‐3‐yl)‐21H,23H‐porphinato(2?)‐κ⁵N²¹,N²²,N²³,N²⁴:N⁵], [MnCl(C₄₀H₂₄N₈)]_n, 1 , was prepared by the hydrothermal reaction of manganese chloride with 5,10,15,20‐tetrakis(pyridin‐3‐yl)‐21H,23H‐porphine. The crystal structure was determined by single‐crystal X‐ray diffraction. The porphyrin macrocycle exhibits a saddle‐like distortion geometry. The Mn^III atom has a six‐coordination geometry. Each porphyrin unit links to two neighbouring units to yield a one‐dimensional coordination polymer. These chains are further interlinked by hydrogen bonds to form a two‐dimensional network. The complex shows red photoluminescence emission bands in ethanol solution, which can be attributed to ligand‐to‐ligand charge transfer (LLCT) accompanied by partial metal‐to‐ligand charge transfer (MLCT), as revealed by TDDFT calculations.     

A one‐dimensional nickel(II) coordination polymer containing 2,6‐dipicolinate and dipyrido[3,2‐a:2′,3′‐c]phenazine

A new coordination polymer, catena‐poly[[(dipyrido[3,2‐a:2′,3′‐c]phenazine‐κ²N,N′)nickel(II)]‐μ‐2,6‐dipicolinato‐κ⁴O²,N,O⁶:O^2′], [Ni(C₇H₃NO₄)(C₁₈H₁₀N₄)]_n, exhibits a one‐dimensional structure in which 2,6‐dipicolinate acts as a bridging ligand interconnecting adjacent nickel(II) centers to form a chain structure. The asymmetric unit contains one Ni^II center, one dipyrido[3,2‐a:2′,3′‐c]phenazine ligand and one 2,6‐dipicolinate ligand. Each Ni^II center is six‐coordinated and surrounded by three N atoms and three O atoms from one dipyrido[3,2‐a:2′,3′‐c]phenazine ligand and two different 2,6‐dipicolinate ligands, leading to a distorted octahedral geometry. Adjacent chains are linked by π–π stacking interactions and weak interactions to form a three‐dimensional supramolecular network.     

A novel three‐dimensional AgI coordination polymer based on mixed naphthalene‐1,5‐disulfonate and aminoacetate ligands

The three‐dimensional coordination polymer poly[[bis(μ₃‐2‐aminoacetato)di‐μ‐aqua‐μ₃‐(naphthalene‐1,5‐disulfonato)‐hexasilver(I)] dihydrate], {[Ag₆(C₁₀H₆O₆S₂)(C₂H₄NO₂)₄(H₂O)₂]·2H₂O}_n, based on mixed naphthalene‐1,5‐disulfonate (L1) and 2‐aminoacetate (L2) ligands, contains two Ag^I centres (Ag1 and Ag4) in general positions, and another two (Ag2 and Ag3) on inversion centres. Ag1 is five‐coordinated by three O atoms from one L1 anion, one L2 anion and one water molecule, one N atom from one L2 anion and one Ag^I cation in a distorted trigonal–bipyramidal coordination geometry. Ag2 is surrounded by four O atoms from two L2 anions and two water molecules, and two Ag^I cations in a slightly octahedral coordination geometry. Ag3 is four‐coordinated by two O atoms from two L2 anions and two Ag^I cations in a slightly distorted square geometry, while Ag4 is also four‐coordinated by two O atoms from one L1 and one L2 ligand, one N atom from another L2 anion, and one Ag^I cation, exhibiting a distorted tetrahedral coordination geometry. In the crystal structure, there are two one‐dimensional chains nearly perpendicular to one another (interchain angle = 87.0°). The chains are connected by water molecules to give a two‐dimensional layer, and the layers are further bridged by L1 anions to generate a novel three‐dimensional framework. Moreover, hydrogen‐bonding interactions consolidate the network.     

A linear heterometallic bismuth–copper coordination polymer containing two types of organic ligands

In the linear coordination polymer catena‐poly[[[aqua(1,10‐phenanthroline‐κ²N,N′)copper(II)]‐μ‐pyridine‐2,6‐dicarboxylato‐κ⁴O²:O^2′,N,O⁶‐[(nitrato‐κ²O,O′)bismuth(III)]‐μ‐pyridine‐2,6‐dicarboxylato‐κ⁴O²,N,O⁶:O^6′] dihydrate], {[Bi^IIICu^II(C₇H₃NO₄)₂(NO₃)(C₁₂H₈N₂)(H₂O)]·2H₂O}_n, the Bi^III cation is O,N,O′‐chelated by the two pyridine‐2,6‐dicarboxylate ligands and O,O′‐chelated by the nitrate anion, the nine coordinating atoms conferring a tricapped trigonal prismatic environment on the metal centre. Each pyridine‐2,6‐dicarboxylate ligand uses one of its carboxylate O atoms to bind to an aqua(1,10‐phenanthroline)copper(II) unit, the Cu—O dative bonds giving rise to the formation of a ribbon motif. The Cu^II cation exhibits a square‐pyramidal geometry. The ribbon motif propagates along the shortest axis of the triclinic unit cell and the solvent water molecules are hydrogen bonded to the same ribbon.     

A one‐dimensional coordination polymer based on a di‐Schiff base supported trinuclear CuII subunit

A novel one‐dimensional Cu^II coordination polymer, catena‐poly[bis(μ₄‐3‐{[2‐(3‐hydroxy‐2‐oxidobenzylidene)hydrazinylidene]methyl}benzene‐1,2‐diolato)dimethanoltricopper(II)], [Cu₃(C₁₄H₁₀N₂O₄)₂(CH₃OH)₂]_n, (I), was constructed with a di‐Schiff base supported centrosymmetric trinuclear Cu^II subunit. In the subunit, two peripheral symmetry‐related Cu^II cations have square‐pyramidal CuNO₄ geometry and the central third Cu^II cation lies on an inversion centre with octahedral CuN₂O₄ geometry. In (I), each partially deprotonated di‐Schiff base 3‐{[2‐(3‐hydroxy‐2‐oxidobenzylidene)hydrazinylidene]methyl}benzene‐1,2‐diolate ligand (Hbcaz³⁻) acts as a heptadentate ligand to bind the Cu^II centres into chains along the a axis. A centrosymmetric Cu₂O₂ unit containing an asymmetrically bridging O atom, being axial at one Cu atom and equatorial at the other Cu atom, links the trinuclear Cu^II subunit into a one‐dimensional chain, which is reinforced by intramolecular phenol–methanol O—H...O and methanol–phenolate O—H...O hydrogen bonds. Interchain π–π stacking interactions between pyrocatechol units, with a distance of 3.5251 (18) Å, contribute to the stability of the crystal packing.