A two‐dimensional coordination polymer: poly[diaqua(μ4‐4,4′‐oxydibenzoato)(μ2‐4,4′‐oxydibenzoato)dilead(II)]

In a new two‐dimensional coordination polymer, [Pb(C₁₄H₈O₅)(H₂O)]_n, the asymmetric unit consists of a Pb^II cation, two halves of two crystallographically distinct fully deprotonated 4,4′‐oxydibenzoate ligands and one aqua ligand. Single‐crystal X‐ray diffraction analysis reveals that the compound is a coordination polymer with the point symbol {5³}₂{5⁴.8²}. In addition, it exhibits a strong fluorescence emission in the solid state at room temperature.     

Poly[[aqua‐μ3‐2,2‐dimethylmalonato‐copper(II)] monohydrate] and poly[aqua‐μ3‐2,2‐dimethylmalonato‐copper(II)]

The coordination mode of the dimethylmalonate ligand in the two title Cu^II complexes, {[Cu(C₅H₃O₄)(H₂O)]·H₂O}_n, (I), and [Cu(C₅H₃O₄)(H₂O)]_n, (II), is the same, with chelated six‐membered, bis‐monodentate and bridging bonding modes. However, the coordination environment of the Cu^II atoms, the connectivity of their metal–organic frameworks and their hydrogen‐bonding interactions are different. Complex (I) has a perfect square‐pyramidal Cu^II environment with the aqua ligand in the apical position, and only one type of square grid consisting of Cu^II atoms linked via carboxylate bridges to three dimethylmalonate ligands, with weak hydrogen‐bond interactions within and between its two‐dimensional layers. Complex (II) has a coordination geometry that is closer to square pyramidal than trigonal bipyramidal for its Cu^II atoms with the aqua ligand now in the basal plane. Its two‐dimensional layer structure comprises two alternating grids, which involve two and four different dimethylmalonate anions, respectively. There are strong hydrogen bonds only within its layers.     

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.     

In situ single‐crystal to single‐crystal (SCSC) transformation of the one‐dimensional polymer catena‐poly[[diaqua(sulfato)copper(II)]‐μ2‐glycine] into the two‐dimensional polymer poly[μ2‐glycine‐μ4‐sulfato‐copper(II)]

The one‐dimensional coordination polymer catena‐poly[diaqua(sulfato‐κO)copper(II)]‐μ₂‐glycine‐κ²O:O′], [Cu(SO₄)(C₂H₅NO₂)(H₂O)₂]_n, (I), was synthesized by slow evaporation under vacuum of a saturated aqueous equimolar mixture of copper(II) sulfate and glycine. On heating the same blue crystal of this complex to 435 K in an oven, its aspect changed to a very pale blue and crystal structure analysis indicated that it had transformed into the two‐dimensional coordination polymer poly[(μ₂‐glycine‐κ²O:O′)(μ₄‐sulfato‐κ⁴O:O′:O′′:O′′)copper(II)], [Cu(SO₄)(C₂H₅NO₂)]_n, (II). In (I), the Cu^II cation has a pentacoordinate square‐pyramidal coordination environment. It is coordinated by two water molecules and two O atoms of bridging glycine carboxylate groups in the basal plane, and by a sulfate O atom in the apical position. In complex (II), the Cu^II cation has an octahedral coordination environment. It is coordinated by four sulfate O atoms, one of which bridges two Cu^II cations, and two O atoms of bridging glycine carboxylate groups. In the crystal structure of (I), the one‐dimensional polymers, extending along [001], are linked via N—H...O, O—H...O and bifurcated N—H...O,O hydrogen bonds, forming a three‐dimensional framework. In the crystal structure of (II), the two‐dimensional networks are linked via bifurcated N—H...O,O hydrogen bonds involving the sulfate O atoms, forming a three‐dimensional framework. In the crystal structures of both compounds, there are C—H...O hydrogen bonds present, which reinforce the three‐dimensional frameworks.     

A three‐dimensional lead(II) coordination polymer: poly[aqua‐μ‐imidazole‐4,5‐dicarboxyl­ato‐lead(II)]

In the title coordination polymer, [Pb(C₅H₂N₂O₄)(H₂O)]_n, the Pb^II atom is seven‐coordinated by one N atom and five O atoms from four individual imidazole‐4,5‐dicarboxyl­ate (HIDC²⁻) groups and one water mol­ecule. It is inter­esting to note that the HIDC²⁻ group serves as a bridging ligand to link the Pb^II atoms into a three‐dimensional microporous open‐framework.     

A three‐dimensional supramolecular vanadium hydroxylamide complex: poly[di‐μ2‐aqua‐bis(hydroxylamido)‐μ3‐malonato‐oxidosodiumvanadium(V)]

The crystal structure of the title compound, [NaV(C₃H₂O₄)(NH₂O)₂O(H₂O)₂], is built up of NaO₆ and VO₅N₂ polyhedra connected through malonate bridges. The NaO₆ octahedra are linked by edge sharing in the equatorial plane to form one‐dimensional infinite chains. These chains are linked together by the malonate bridges to form two‐dimensional layers. The distorted VO₅N₂ pentagonal bipyramid is grafted on to the layer by a malonate carboxylate O atom. Adjacent layers are connected through O—H...O and N—H...O hydrogen bonds to build up a three‐dimensional supramolecular structure.     

A three‐dimensional PbII coordination framework: poly[[μ4‐(E)‐2,2′‐(diazene‐1,2‐diyl)dibenzoato]dimethanollead(II)]

In the title coordination polymer, [Pb(C₁₄H₈N₂O₄)(CH₃OH)₂]_n, the asymmetric unit contains half of a Pb^II cation, half of a 2,2′‐(diazene‐1,2‐diyl)dibenzoate dianionic ligand (denoted L²⁻) and one methanol ligand. Each Pb^II centre is eight‐coordinated by six O atoms of chelating/bridging carboxylate groups from four L²⁻ ligands and two O atoms from two terminal methanol ligands, forming a distorted dodecahedron. The [PbL₂(MeOH)₂] subunits are interlinked via the sharing of two carboxylate O atoms to form a one‐dimensional [PbL₂(MeOH)₂]_n chain. Adjacent chains are further connected by L²⁻ ligands, giving rise to a two‐dimensional layer, and these layers are bridged by L²⁻ linkers to afford a three‐dimensional framework with a 4¹²6³ topology.     

A novel three‐dimensional heterometallic coordination polymer: poly[[diaquadi‐μ3‐chlorido‐μ2‐chlorido‐tri‐μ3‐nicotinato‐tricopper(I)gadolinium(III)] hemihydrate]

In the title polymeric heterometallic compound, {[Cu₃Gd(C₆H₄NO₂)₃Cl₃(H₂O)₂]·0.5H₂O}_n, comprising copper(I) and gadolinium(III) cations bridged by nicotinate (nic) ligands and chloride anions, the Gd^III centers display a bicapped trigonal prismatic geometry, defined by six carboxylate O atoms and two water molecules. For copper(I), one Cu center is three‐coordinated by three chloride ions and displays a trigonal–planar geometry; the other two Cu centers are four‐coordinated and display a very distorted tetrahedral geometry. The chloride anions act in μ₂‐ and μ₃‐bridging modes, linking the Cu^I ions into an infinite chain. The nic ligand exhibits a tridentate coordination mode, with the carboxylate O atoms linking to two Gd^III ions and the N atom linking to one Cu^I ion. Thus, a novel three‐dimensional heterometallic coordination polymer is constructed from Gd–carboxylate subunits and Cu—Cl chains. In addition, intra‐ and intermolecular O—H...O and O—H...Cl hydrogen bonds are also observed within the three‐dimensional structure. Topologically, the framework represents an unusual 3,6‐connected (4.8²)₃(4¹⁰.6⁵) net.     

The first three‐dimensional FeIII–SrII heterometallic coordination polymer: poly[[diaquatetrakis(μ3‐pyridine‐2,3‐dicarboxylato)diiron(III)strontium(II)] dihydrate]

The title compound, poly[[diaqua‐1κ²O‐tetrakis(μ₃‐pyridine‐2,3‐dicarboxylato)‐2:1:2′κ¹⁰N,O²:O^2′,O³:O^3′;2:1:2′κ⁸O³:O^3′:N,O²‐diiron(III)strontium(II)] dihydrate], {[Fe₂Sr(C₇H₃O₄)₄(H₂O)₂]·2H₂O}_n, which has triclinic (P) symmetry, was prepared by the reaction of pyridine‐2,3‐dicarboxylic acid, SrCl₂·6H₂O and Fe(OAc)₂(OH) (OAc is acetate) in the presence of imidazole in water at 363 K. In the crystal structure, the pyridine‐2,3‐dicarboxylate (pydc²⁻) ligand exhibits μ₃‐η¹,η¹:η¹:η¹ and μ₃‐η¹,η¹:η¹,η¹:η¹ coordination modes, bridging two Fe^III cations and one Sr^II cation. The Sr^II cation, which is located on an inversion centre, is eight‐coordinated by six O atoms of four pydc²⁻ ligands and two water molecules. The coordination geometry of the Sr^II cation can be best described as distorted dodecahedral. The Fe^III cation is six‐coordinated by O and N atoms of four pydc²⁻ ligands in a slightly distorted octahedral geometry. Each Fe^III cation bridges two neighbouring Fe^III cations to form a one‐dimensional [Fe₂(pydc)₄]_n chain. The chains are connected by Sr^II cations to form a three‐dimensional framework. The topology type of this framework is tfj . The structure displays O—H...O and C—H...O hydrogen bonding.     

A novel one‐dimensional coordination polymer,catena‐poly[[diaquacobalt(II)]‐μ‐(2,2′‐bipyridyl‐3,3′‐dicarboxylato‐κ4N,N′:O,O′)]

The title compound, [Co(C₁₂H₆N₂O₄)(H₂O)₂]_n, has been hydro­thermally synthesized and structurally characterized. It consists of polymeric chains of [Co{μ‐(2,2′‐bipyridyl‐3,3′‐di­carboxyl­ato‐κ⁴N,N′:O,O′)}(H₂O)₂] units, in which each Co^II cation is octahedrally coordinated by two chelating pyridyl N atoms, two chelating carboxyl O atoms from different carboxylate groups of another bipyridyl ligand, and two water mol­ecules as terminal ligands. A crystallographic twofold axis parallel to the chain axis, passes through the Co atom.     

A one‐dimensional CdII coordination polymer: catena‐poly[cadmium(II)‐bis(μ‐6‐methylpicolinato)]

In the title compound, [Cd(C₇H₆NO₂)₂]_n, the Cd^II ion has a distorted octahedral geometry. The 6‐methylpyridine‐2‐carboxylate anions are perpendicular to one another and act as bidentate and bridging ligands. Two carboxylate O atoms bridge the Cd^II ions, forming centrosymmetric dinuclear units. These units are further connected via carboxylate O atoms into a one‐dimensional polymeric chain which extends in the [100] direction.     

A one‐dimensional coordination polymer based on Cd2O2 clusters: poly[aqua(μ3‐4,4′‐sulfonyldibenzoato)(3,4,7,8‐tetramethyl‐1,10‐phenanthroline‐κ2N,N′)cadmium(II)]

In the title mixed‐ligand metal–organic polymeric complex [Cd(C₁₄H₈O₆S)(C₁₆H₁₆N₂)(H₂O)]_n, the asymmetric unit contains a crystallographically unique Cd^II atom, one doubly deprotonated 4,4′‐sulfonyldibenzoic acid ligand (H₂SDBA), one 3,4,7,8‐tetramethyl‐1,10‐phenanthroline (TMPHEN) molecule and one water molecule. Each Cd^II centre is coordinated by two N atoms from the chelating TMPHEN ligand, three O atoms from monodentate carboxylate groups of three different SDBA²⁻ ligands and one O atom from a coordinated water molecule, giving a distorted CdN₂O₄ octahedral geometry. Single‐crystal X‐ray diffraction analysis reveals that the compound is a one‐dimensional double‐chain polymer containing 28‐membered rings based on Cd₂O₂ clusters, with a Cd...Cd separation of 3.6889 (4) Å. These chains are linked by O—H...O and C—H...O hydrogen bonds to form a three‐dimensional supramolecular framework. The framework is reinforced by π–π and C—O...π interactions.     

Four (2,2′‐bipyridyl)(ferrocenyl)boronium derivatives

Crystal structures are reported for four (2,2′‐bipyridyl)(ferrocenyl)boronium derivatives, namely (2,2′‐bipyridyl)(ethenyl)(ferrocenyl)boronium hexafluoridophosphate, [Fe(C₅H₅)(C₁₇H₁₅BN₂)]PF₆, (Ib), (2,2′‐bipyridyl)(tert‐butylamino)(ferrocenyl)boronium bromide, [Fe(C₅H₅)(C₁₉H₂₂BN₃)]Br, (IIa), (2,2′‐bipyridyl)(ferrocenyl)(4‐methoxyphenylamino)boronium hexafluoridophosphate acetonitrile hemisolvate, [Fe(C₅H₅)(C₂₂H₂₀BN₃O)]PF₆·0.5CH₃CN, (IIIb), and 1,1′‐bis[(2,2′‐bipyridyl)(cyanomethyl)boronium]ferrocene bis(hexafluoridophosphate), [Fe(C₁₇H₁₄BN₃)₂](PF₆)₂, (IVb). The asymmetric unit of (IIIb) contains two independent cations with very similar conformations. The B atom has a distorted tetrahedral coordination in all four structures. The cyclopentadienyl rings of (Ib), (IIa) and (IIIb) are approximately eclipsed, while a bisecting conformation is found for (IVb). The N—H groups of (IIa) and (IIIb) are shielded by the ferrocenyl and tert‐butyl or phenyl groups and are therefore not involved in hydrogen bonding. The B—N(amine) bond lengths are shortened by delocalization of π‐electrons. In the cations with an amine substituent at boron, the B—N(bipyridyl) bonds are 0.035 (3) Å longer than in the cations with a methylene C atom bonded to boron. A similar lengthening of the B—N(bipyridyl) bonds is found in a survey of related cations with an oxy group attached to the B atom.     

A novel three‐dimensional CdII coordination polymer: poly[[aquabis(2,2′‐bipyridine)(μ5‐pyrazol‐1‐ide‐3,5‐dicarboxylato)(μ4‐pyrazol‐1‐ide‐3,5‐dicarboxylato)(μ3‐pyrazole‐3,5‐dicarboxylato)tetracadmium(II)] dihydrate]

The title compound, {[Cd₄(C₅H₂N₂O₄)(C₅HN₂O₄)₂(C₁₀H₈N₂)₂(H₂O)]·2H₂O}_n, crystallized in the monoclinic space group P2₁/n and displays a three‐dimensional architecture. The asymmetric unit is composed of four crystallographically independent Cd^II centres, two triply deprotonated pyrazole‐3,5‐dicarboxylic acid molecules, one doubly deprotonated pyrazole‐3,5‐dicarboxylic acid molecule, two 2,2′‐bipyridine ligands, one coordinated water molecule and two interstitial water molecules. Interestingly, the Cd^II centers exhibit two different coordination numbers. Two Cd^II centres adopt a distorted octahedral arrangement and a third a trigonal–prismatic geometry, though they are all hexacoordinated. However, the fourth Cd^II center is heptacoordinated and displays a pentagonal–bipyramidal geometry. The three anionic ligands adopt μ₃‐, μ₄‐ and μ₅‐bridging modes, first linking Cd^II centers into a one‐dimensional wave‐like band, then into a wave‐like layer and finally into a three‐dimensional coordination framework, which is stabilized by hydrogen bonds.     

A novel three‐dimensional heterometallic coordination polymer: poly[[hexaaquabis[μ3‐3,5‐dicarboxylatopyrazolato‐κ5O3,N2:N1,O5:O5′](μ2‐oxalato‐κ4O1,O2:O1′,O2′)copper(II)dierbium(III)] trihydrate]

The title novel heterometallic 3d–4f coordination polymer, {[CuEr₂(C₅HN₂O₄)₂(C₂O₄)(H₂O)₆]·3H₂O}_n, has a three‐dimensional metal–organic framework composed of two types of metal atoms (one Cu^II and two Er^III) and two types of bridging anionic ligands [3,5‐dicarboxylatopyrazolate(3−) (ptc³⁻) and oxalate]. The Cu^II atom is four‐coordinated in a square geometry. The Er^III atoms are both eight‐coordinated, but the geometries at the two atoms appear different, viz. triangular dodecahedral and bicapped trigonal prismatic. One of the oxalate anions is located on a twofold axis and the other lies about an inversion centre. Both oxalate anions act as bis‐bidentate ligands bridging the latter type of Er atoms in parallel zigzag chains. The pdc³⁻ anions act as quinquedentate ligands not only chelating the Cu^II and the triangular dodecahedral Er^III centres in a bis‐bidentate bridging mode, but also connecting to Er^III centres of both types in a monodentate bridging mode. Thus, a three‐dimensional metal–organic framework is generated, and hydrogen bonds link the metal–organic framework with the uncoordinated water molecules. This study describes the first example of a three‐dimensional 3d–4f coordination polymer based on pyrazole‐3,5‐dicarboxylate and oxalate, and therefore demonstrates further the usefulness of pyrazoledicarboxylate as a versatile multidentate ligand for constructing heterometallic 3d–4f coordination polymers with interesting architectures.     

catena‐Poly[[(2,2′‐bipyridyl)oxidovanadium]‐di‐μ2‐oxido‐[(2,2′‐bipyridyl)oxidovanadium]‐μ3‐selenito‐bis[(2,2′‐bipyridyl)dioxidovanadium]‐μ3‐selenito]

In the title compound, [V₄O₈(SeO₃)₂(C₁₀H₈N₂)₄], there are two distinct vanadium coordination environments. Alternating corner‐shared VO₄N₂ octahedra and SeO₃ pyramids result in eight‐membered centrosymmetric V₂Se₂O₄ rings. In addition, pairs of V centres form centrosymmetric V₂O₆N₄ clusters via edge‐sharing. These two kinds of secondary building units are linked in an ABABAB fashion to give an infinite chain whose nature is unprecedented in Se–V–O systems.     

The three‐dimensional coordination polymer poly[[aqua[μ4‐2,2′‐(diazene‐1,2‐diyl)dibenzoato]lead(II)] 1,2‐bis(pyridin‐4‐yl)ethylene hemisolvate]

A novel three‐dimensional coordination polymer, {[Pb(C₁₄H₈N₂O₄)(H₂O)]·0.5C₁₂H₁₀N₂}_n, has been synthesized by hydrothermal reaction of Pb(OAc)₂·3H₂O (OAc is acetate), 2,2′‐(diazene‐1,2‐diyl)dibenzoic acid (H₂L) and 1,2‐bis(pyridin‐4‐yl)ethylene (bpe). The asymmetric unit contains a crystallographically independent Pb^II cation, one L²⁻ ligand, an aqua ligand and half a bpe molecule. Each Pb^II centre is seven‐coordinated by six O atoms of bridging–chelating carboxylate groups from L²⁻ ligands and by one O atom from a coordinated water molecule. The Pb^II cations are bridged by L²⁻ ligands, forming [PbO₂]_n chains along the a axis. These chains are further connected by L²⁻ ligands along the b and c axes to give a three‐dimensional framework with a 4¹²6³ topology. The channel voids are occupied by bpe molecules.     

Poly[[diaqua(μ3‐2,2‐dimethylmalonato)cadmium(II)] tetrahydrate]

In the title complex, {[Cd(C₅H₆O₄)(H₂O)₂]·4H₂O}_n, the dimethylmalonate–cadmium metal–organic framework co‐exists with an extended structure of water molecules, which resembles a sodalite‐type framework. In the asymmetric unit, there are five independent solvent water molecules, two of which are in special positions. The Cd atoms are eight‐coordinated in a distorted square‐antiprismatic geometry by six O atoms of three different dimethylmalonate groups and by two water molecules, and form a two‐dimensional honeycomb layer parallel to the bc plane. Two such layers sandwich the hydrogen‐bonded water layer, which has a sodalite‐type structure with truncated sodalite units composed of coordinated and solvent water molecules. This work is the first example of a dimethylmalonate cadmium complex containing truncated sodalite‐type water clusters.     

Di‐μ‐acetato‐bis­[bis(4‐amino­benzoato)(2,2′‐bipyridyl)­manganese(II)]

In the title compound, [Mn₂(C₇H₆NO₂)₂(C₂H₃O₂)₂(C₁₀H₈N₂)₂], the two Mn^II atoms are each coordinated by one 2,2′‐bi­pyridyl mol­ecule, one 4‐amino­benzoate ion and two acetate ions. The two Mn atoms exhibit different coordination environments: one is coordinated by two N and four O atoms, while the other is coordinated by two N and three O atoms. The two Mn atoms are bridged by two acetate ions in a syn–anti mode, with an Mn⋯Mn distance of 4.081 (1) Å.     

The two‐dimensional coordination polymer poly[diaqua(μ2‐1H‐imidazo[4,5‐f][1,10]phenanthroline)‐μ4‐sulfato‐μ3‐sulfato‐dicadmium(II)]

In the title coordination polymer, [Cd₂(SO₄)₂(C₁₃H₈N₄)(H₂O)₂]_n, there are two crystallographically independent Cd^II centres with different coordination geometries. The first Cd^II centre is hexacoordinated by four O atoms of four sulfate ligands, one water O atom and one N atom of a 1H‐imidazo[4,5‐f][1,10]phenanthroline (IP) ligand, giving a distorted octahedral coordination environment. The second Cd^II centre is heptacoordinated by four O atoms of three sulfate ligands, one water O atom and two N atoms of one chelating IP ligand, resulting in a distorted monocapped anti‐trigonal prismatic geometry. The symmetry‐independent Cd^II ions are bridged in an alternating fashion by sulfate ligands, forming one‐dimensional ladder‐like chains which are connected through the IP ligands to form two‐dimensional layers. These two‐dimensional layers are linked by interlayer hydrogen bonds, leading to the formation of a three‐dimensional supramolecular network.