Heteropolynuclear Sodium(I) Lead(II) Complex: Crystal and Molecular Structure of a Novel 3‐D Polymer, [(en)Pb(μ3‐ONO)2Na(μ3‐ONO)2Na(μ‐O2ClO2)Na]n

A novel 3D polymeric heteropolynuclear sodium(I) lead(II) complex containing different ligands, [NaPb(ClO₄)(en)(NO₂)₂] was synthesized and characterized by elemental analysis and IR, and ¹H‐, ¹³C‐, and ²⁰⁷Pb‐NMR spectroscopy. The single‐crystal X‐ray data of [NaPb(ClO₄)(en)(NO₂)₂]_n established that the complex is a three‐dimensional polymer, [(en)Pb(μ₃‐ONO)₂Na(μ₃‐ONO)₂Na(μ‐O₂ClO₂)Na]_n. The Pb and Na atoms have four‐ and eight‐coordinate geometry, respectively. The lone pair of electrons at the Pb^II atom is ‘stereochemically active’.     

A Three—Dimensional Lead(II) Polymer with Bridging Saccharinate and Unusually Coordinated Acetate Ligands — Synthesis,IR Spectra,and Crystal Structure of [Pb(H2O)(μ‐OAc)(μ‐sac)]n

The complex [Pb(H₂O)(μ‐OAc)(μ‐sac)]n with acetate (OAc) and saccharinate (sac) ligands was characterized by IR, elemental analysis and X‐ray crystallography. The mixed‐anion lead(II) complex crystallizes in the triclinic crystal system with the space group of P1¯. The single crystal X‐ray analysis shows that the complex is a coordination polymer in which the lead(II) ions have a highly distorted pentagonal bipyramidal coordination geometry. Lead(II) ions are bridged by carboxylate groups in a zigzag arrangement forming one‐dimensional infinite chains, which are also linked by sac bridges and aromatic π‐π contacts between the adjacent phenyl rings of sac ligands, resulting in a three‐dimensional network. One water molecule coordinates the lead(II) ion and also forms weak hydrogen bonds with the sulfonyl oxygen atoms of the neighboring sac ligands. The sac ligand acts as a bridging ligand through the nitrogen and carbonyl oxygen atoms, while the carboxylate moiety of the acetate ligand shows an unusual (bidentate, and bridging) coordination behaviour, which was observed for the first time in the structure.     

Direct Synthesis of PbO Nanoparticles From a Lead(II) Nano Coordination Polymer Precursor: Synthesis,Crystal Structure,and DFT Calculations of [Pb2(dmp)2(μ‐N3)2(μ‐ClO4)2]n with the First Pb2‐(μ‐ClO4)2 Unit

Nanostructures of a new coordination polymer of divalent lead with the ligand 2, 9‐dimethyl‐1, 10‐phenanthroline (dmp) containing the first Pb₂‐(μ‐ClO₄)₂ motif, [Pb₂(dmp)₂(μ‐N₃)₂(μ‐ClO₄)₂]_n ( 1 ), was synthesized by a sonochemical method that produces the coordination polymers at nano size. The new nanostructure was characterized by scanning electron microscopy, X‐ray powder diffraction, IR, ¹H NMR and ¹³C NMR spectroscopy, and elemental analysis. Compound 1 was structurally characterized by single‐crystal X‐ray diffraction and the single‐crystal X‐ray data shows that the coordination number of Pb^II ions is six, (PbN₄O₂), with two N‐donor atoms from aza‐aromatic base ligands and four O‐donors from two perchlorate anions and two N‐donors from two azide anions. It has a “stereo‐chemically active” electron lone pair, and the coordination sphere is hemidirected. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The chains interact with each other through π–π stacking interactions creating a 3D framework. The structure of the title complex was optimized by density functional theory calculations. Calculated structural parameters and IR spectra for the title complex are in agreement with the crystal structure. The PbO nanoparticles were obtained by thermolysis of 1 at 180 °C with oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by the Scherrer equation to be 23 nm. The morphology and size of the prepared PbO samples were further observed using SEM.     

A Novel 1D Coordination Polymer [Pb(phen)(μ‐N3)(μ‐NO3)]n with the First Pb2‐(μ‐N3)2 Unit (phen = 1,10‐phenanthroline)

A novel 1D polymeric lead(II) complex containing the first Pb₂‐(μ‐N₃)₂ motif, [Pb(phen)(μ‐N₃)(μ‐NO₃)]_n (phen = 1,10‐phenanthroline), has been synthesized and characterized. The single‐crystal X‐ray data showed the coordination number of Pb²⁺ ions to be eight (PbN₄O₄) with the Pb²⁺ ions having “stereo‐chemically active” electron lone pairs; the coordination sphere is hemidirected. The chains interact with each other via π‐π interactions to create a 3D framework.     

One‐Dimensional Holodirected Lead(II) Coordination Polymer, [Pb(μ2‐TPPZ)(NO3)(ClO4)]n (TPPZ = 2, 3, 5, 6–tetra(2‐pyridyl)pyrazine)

A lead(II) complex with 2,3,5,6‐tetra(2‐pyridyl)pyrazine (TPPZ), nitrate, and perchlorate ligands has been synthesized and characterized by CHN elemental analysis and IR and ²⁰⁷Pb NMR spectroscopy. The single crystal X‐ray data of the [Pb₂(μ‐TPPZ)₂(NO₃)₂(ClO₄)₂] compound show that the complex is a one‐dimensional coordination polymer and that the Lead atom has a less‐common, ten‐coordinate holodirected geometry.     

Poly[tetraamminecopper(II) bis[tris(μ2‐cyanido‐κ2C,N)dicuprate(I)]]: a unique CuI–CuII mixed‐valence complex containing anionic cuprous cyanide layers and [Cu(NH3)4]2+ cations

The title compound, {[Cu(NH₃)₄][Cu(CN)₃]₂}_n, features a Cu^I–Cu^II mixed‐valence CuCN framework based on {[Cu₂(CN)₃]⁻}_n anionic layers and [Cu(NH₃)₄]²⁺ cations. The asymmetric unit contains two different Cu^I ions and one Cu^II ion which lies on a centre of inversion. Each Cu^I ion is coordinated to three cyanide ligands with a distorted trigonal–planar geometry, while the Cu^II ion is ligated by four ammine ligands, with a distorted square‐planar coordination geometry. The interlinkage between Cu^I ions and cyanide bridges produces a honeycomb‐like {[Cu₂(CN)₃]⁻}_n anionic layer containing 18‐membered planar [Cu(CN)]₆ metallocycles. A [Cu(NH₃)₄]²⁺ cation fills each metallocyclic cavity within pairs of exactly superimposed {[Cu₂(CN)₃]⁻}_n anionic layers, but there are no cations between the layers of adjacent pairs, which are offset. Pairs of N—H...N hydrogen‐bonding interactions link the N—H groups of the ammine ligands to the N atoms of cyanide ligands.     

Poly[bis(μ3‐5′‐carboxy‐2,2′‐bipyridine‐5‐carboxylato‐κ4O:N,N′:O′)lead(II)]

The title compound, [Pb(C₁₂H₇N₂O₄)₂]_n, obtained by reaction of Pb(NO₃)₂ and 2,2′‐bipyridine‐5,5′‐dicarboxylic acid (H₂bptc) under hydrothermal conditions, has a structure in which the unique Pb^II cation sits on a twofold axis and is octa‐coordinated by four O‐atom donors from four Hbptc⁻ ligands and four N‐atom donors from two Hbptc⁻ ligands in a distorted dodecahedral geometry. With each Pb^II cation connected to six Hbptc⁻ ligands and each Hbptc⁻ ligand bridging three Pb^II cations, a three‐dimensional polymeric structure is formed. From a topological point of view, the three‐dimensional net is binodal, with six‐connected (the Pb^II cation) and three‐connected (the Hbptc⁻ ligand) nodes, resulting in a distorted rutile (4².8)₂(4⁴8⁹12²) topology.     

The coordination polymer poly[bis[μ2‐2‐(2,2′‐bi‐1H‐imidazol‐1‐yl)acetato]cadmium]

The title compound, [Cd(C₈H₇N₄O₂)₂]_n, crystallizes in the centrosymmetric triclinic space group P with an asymmetric unit consisting of a bivalent Cd^II atom and two 2‐(2,2′‐bi‐1H‐imidazol‐1‐yl)acetate (BDAC⁻) anions. Two inversion‐related BDAC⁻ ligands are oppositely arranged and bind two Cd^II ions to form a [Cd₂(BDAC)₂] rhomboid subunit which is bridged by another BDAC⁻ ligand to form an infinite ladder along the a direction containing parallelogram grids. The three‐dimensional supramolecular architecture is formed by hydrogen bonds and C—H...π and π–π interactions.     

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.     

Synthesis,Crystal Structures and Properties of Tetrametallic Complexes: [M2(phen)4(FCA)2](ClO4)2·(H2O)2 (M=Zn or Co,phen=1,10‐phenanthroline,FCA=anion of 3‐ferrocenyl‐2‐crotonic acid)

Two new complexes [Zn₂(phen)₄(FCA)₂](ClO₄)₂·(H₂O)₂ ( 1 ) and [Co₂(phen)₄ (FCA)₂](ClO₄)₂·(H₂O)₂ (2) (FCA=anion of 3‐ferrocenyl‐2‐crotonic acid, phen=1,10‐phenanthroline) have been synthesized, and characterized by elemental analysis, IR, UV‐Vis spectra, thermal analyses, and single‐crystal X‐ray diffraction. Two M(II) (M=Zn or Co) ions are bridged by two FCA anions with syn‐anti bridging ligands, leading to dimeric cores, [M₂(phen)₄(FCA)₂]²⁺, and each M(II) ion is six‐coordinated in a distorted octahedral geometry by two chelate phen ligands and two μ₂‐carboxylate oxygen atoms from two FCA groups. The M(II)…M(II) intradimer distances are 0.4391 and 0.4462 nm in 1 and 2 , respectively. Electrochemical properties of the complexes have been discussed.     

Poly[aqua­(μ3‐benzene‐1,2‐dicarboxyl­ato)(μ2‐hydroxo)indium(III)]

In the title compound, [In(C₈H₄O₄)(OH)(H₂O)]_n, the coordination of the In^III ion is composed of six O atoms from three dianionic benzene‐1,2‐dicarboxylate ligands, two hydroxyl groups and one coordinated water mol­ecule in a distorted octa­hedral geometry. The In³⁺ ions are linked by the hydroxyl groups to form zigzag In–OH–In chains, which are further bridged by the benzene‐1,2‐dicarboxylic acid ligands to generate a two‐dimensional layered structure featuring three types of rings (six‐, 14‐ and 20‐membered). Hydrogen bonds between the water mol­ecule and a carboxyl­ate O atom, and between the hydroxyl group and a carboxyl­ate O atom, are observed within the layers. In the crystal packing, there are π–­π stacking inter­actions between the benzene rings of adjacent layers, with a centroid‐to‐centroid distance of 3.668 (3) Å and a dihedral angle of 4.8 (2)°.     

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 new one‐dimensional nickel metal–organic framework: catena‐poly[[[diaquabis(4‐{[(1‐phenyl‐1H‐tetrazol‐5‐yl)sulfanyl]methyl}benzoato‐κO)nickel(II)]‐μ‐4,4′‐bipyridine‐κ2N:N′] monohydrate]

The title complex, {[Ni(C₁₅H₁₁N₄O₂S)₂(C₁₀H₈N₂)(H₂O)₂]·H₂O}_n, was synthesized by the reaction of nickel chloride, 4‐{[(1‐phenyl‐1H‐tetrazol‐5‐yl)sulfanyl]methyl}benzoic acid (HL) and 4,4′‐bipyridine (bpy) under hydrothermal conditions. The asymmetric unit contains two half Ni^II ions, each located on an inversion centre, two L⁻ ligands, one bpy ligand, two coordinated water molecules and one unligated water molecule. Each Ni^II centre is six‐coordinated by two monodentate carboxylate O atoms from two different L⁻ ligands, two pyridine N atoms from two different bpy ligands and two terminal water molecules, displaying a nearly ideal octahedral geometry. The Ni^II ions are bridged by 4,4′‐bipyridine ligands to afford a linear array, with an Ni...Ni separation of 11.361 (1) Å, which is further decorated by two monodentate L⁻ ligands trans to each other, resulting in a one‐dimensional fishbone‐like chain structure. These one‐dimensional fishbone‐like chains are further linked by O—H...O, O—H...N and C—H...O hydrogen bonds and π–π stacking interactions to form a three‐dimensional supramolecular architecture. The thermal stability of the title complex was investigated via thermogravimetric analysis.     

Poly[(μ2‐aqua‐κ2O:O)(μ3‐azido‐κ3N1:N1:N3)(μ2‐isonicotinato‐κ2O:O′)lead(II)]

In the title compound, [Pb(C₆H₄NO₂)(N₃)(H₂O)]_n, the Pb ion is seven‐coordinated by three N atoms from three azide ligands, two O atoms from two isonicotinate (inic) ligands and two O atoms from two coordinated water molecules, forming a distorted monocapped triangular prismatic coordination geometry. Each azide ligand bridges three Pb^II ions in a μ_1,1,3 coordination mode to form a two‐dimensional three‐connected 6³ topology network extending in the bc plane. The carboxylate group of the inic unit and the aqua ligand act as coligands to bridge Pb^II ions. Adjacent two‐dimensional layers are connected by hydrogen‐bonding interactions between the isonicotinate N atom and the water molecule, resulting in an extended three‐dimensional network. The title complex is the first reported coordination polymer involving a p‐block metal, an azide and a carboxylate.     

Syntheses and Characterization of Mixed‐Anions Lead(II) Complexes, [Pb(phen)2(CH3COO)]X (X=NCS—, NO3— and ClO4—), Crystal Structure of [Pb(phen)2(CH3COO)](ClO4)

The 1:2 adduct lead(II) complexes with 1, 10‐phenanthroline (phen) containing three different anions, [Pb(phen)₂(CH₃COO)X] (X=NCS^—, NO₃^— and ClO₄^—), have been synthesized and characterized by CHN elemental analysis, IR‐, ¹H‐ and ¹³C NMR spectroscopy. The structure of [Pb(phen)₂(CH₃COO)(ClO₄)] was determined by single crystal X‐ray analysis. The Pb atom of the monomeric complex is coordinated by four nitrogen atoms of two 1, 10‐phenanthroline ligands and two oxygen atoms of the acetate ligand to form an irregular octahedron. The arrangement of the 1, 10‐phenanthroline and acetate ligands, exhibits a coordination gap around the Pb^II ion, possibly occupied by a stereochemical electron active lone pair on lead(II), which results in a hemidirected lead compound. The π‐π stacking interaction between the parallel aromatic rings may help to increase the coordination ‘gap’ around the Pb^II ion.     

Poly[μ2‐(N‐hydroxypyridine‐2‐carboxamidine)‐μ2‐nitrato‐silver(I)]

In the title complex, [Ag(NO₃)(C₆H₇N₃O)]_n or [Ag(NO₃)(pyaoxH₂)] (pyaoxH₂ is N‐hydroxypyridine‐2‐carboxamidine), the Ag⁺ ion is bridged by the pyaoxH₂ ligands and nitrate anions, giving rise to a two‐dimensional molecular structure. Each pyaoxH₂ ligand coordinates to two Ag⁺ ions using its pyridyl and carboxamidine N atoms, and the OH and the NH₂ groups are uncoordinated. Each nitrate anion uses two O atoms to coordinate to two Ag⁺ ions. The Ag...Ag separation via the pyaoxH₂ bridge is 2.869 (1) Å, markedly shorter than that of 6.452 (1) Åvia the nitrate bridge. The two‐dimensional structure is fishscale‐like, and can be described as pyaoxH₂‐bridged Ag₂ nodes that are further linked by nitrate anions. Hydrogen bonding between the amidine groups and the nitrate O atoms connects adjacent layers into a three‐dimensional network.     

Poly[hexaaquabis(μ4‐4‐carboxybenzenesulfonato)bis(μ3‐4‐carboxybenzenesulfonato)calcium(II)dipotassium(I)]

This study presents the coordination modes and crystal organization of a calcium–potassium coordination polymer, poly[hexaaquabis(μ₄‐4‐carboxybenzenesulfonato‐κ⁴O¹:O^1′:O^1′′:O⁴)bis(μ₃‐4‐carboxybenzenesulfonato‐κ²O¹:O^1′)calcium(II)dipotassium(I)], [CaK₂(C₇H₅O₅S)₄(H₂O)₆]_n, displaying a novel two‐dimensional framework. The potassium ion is seven‐coordinated by four sulfonate and one carboxyl O atom located on five different acid ligands, two of which are unique, and by two symmetry‐independent water O atoms. A pair of close potassium ions share two inversion‐related sulfonate O‐atom sites to form a dimeric K₂O₁₂ unit, which is extended into a one‐dimensional array along the a‐axis direction. The six‐coordinate Ca²⁺ ion occupies a special position () at (0, , ) and is surrounded by four sulfonate O atoms from two inversion‐related pairs of unique acid monoanions and by two O atoms from aqua ligands. The compound displays a layered structure, with K₂O₁₂ and CaO₆ polyhedra in the layers and aromatic linkers between the layers. The three‐dimensional scaffold is open, with nano‐sized channels along the c axis.     

catena‐Poly[hexaaquamagnesium(II) [bis(μ3‐5‐nitro‐2‐oxidoisophthalato)dicopper(II)] dihydrate]

In the centrosymmetric dinuclear anions of the title bimetallic complex, {[Mg(H₂O)₆][Cu₂(C₈H₂NO₇)₂]·2H₂O}_n, each Cu^II ion is strongly coordinated by four O atoms in a distorted square‐planar geometry. Two of these O atoms belong to phenolate groups and the other two to carboxylate groups from 5‐nitro‐2‐oxidoisophthalate (L1) trianions, derived from 5‐nitrobenzene‐1,2,3‐tricarboxylic acid (O₂N–H₃L). The phenolate O atoms bridge the two Cu^II ions in the anion. In addition, each Cu^II cation interacts weakly with a symmetry‐related carboxylate O atom of an adjacent L1 ligand, giving a square‐pyramidal coordination geometry. The copper residue forms a ladder‐like linear coordination polymer via L1 ligands. The [Mg(H₂O)₆]²⁺ cations sit on centres of inversion. The polymeric anions, cations and free water molecules are self‐assembled into a three‐dimensional supramolecular network via O—H...O hydrogen bonds.     

Poly[tetra‐μ2‐l‐lactato‐indium(III)sodium(I)]

The asymmetric unit of the title compound, [InNa(C₃H₅O₃)₄]_n, consists of one In^III ion, one Na^I ion and four crystallographically independent l ‐lactate monoanions. The coordination of the In^III ion is composed of five carboxylate O and two hydroxy O atoms in a distorted pentagonal–bipyramidal coordination geometry. The Na^I ion is six‐coordinated by four carboxylate O atoms and two hydroxy O atoms from four l ‐lactate ligands in a distorted octahedral geometry. Each In^III ion is coordinated by four surrounding l ‐lactate ligands to form an [In(l ‐lactate)₄]⁻ unit, which is further linked by Na^I ions through Na—O bonds to give a two‐dimensional layered structure. Hydrogen bonds between the hydroxy groups and carboxylate O atoms are observed between neighbouring layers.     

Poly[bis(μ‐benzene‐1,4‐dicarboxylato)bis[μ‐6‐(4‐pyridyl)‐5H‐imidazolo[4,5‐f][1,10]phenanthroline]dilead(II)]: an interpenetrating α‐Po net

The asymmetric unit of the title compound, [Pb₂(C₈H₄O₄)₂(C₁₈H₁₁N₅)₂]_n, contains two Pb^II atoms, two benzene‐1,4‐dicarboxylate (1,4‐bdc) dianions and two 6‐(4‐pyridyl)‐5H‐imidazolo[4,5‐f][1,10]phenanthroline (L) ligands. Each Pb^II atom is eight‐coordinated by three N atoms from two different L ligands and five carboxylate O atoms from three different 1,4‐bdc dianions. The two 1,4‐bdc dianions (1,4‐bdc₁ and 1,4‐bdc₂) show different coordination modes. Each 1,4‐bdc₁ coordinates to two Pb^II atoms in a chelating bis‐bidentate mode. Each carboxylate group of the 1,4‐bdc₂ anion connects two Pb^II atoms in a chelating–bridging tridentate mode to form a dinuclear unit. Neighbouring dinuclear units are connected together by the aromatic backbone of the 1,4‐bdc dianions and the L ligands into a three‐dimensional six‐connected α‐polonium framework. The most striking feature is that two identical three‐dimensional single α‐polonium nets are interlocked with each other, thus leading directly to the formation of a twofold interpenetrated three‐dimensional α‐polonium architecture. The framework is held together in part by strong N—H...O hydrogen bonds between the imidazole NH groups of the L ligands and the carboxylate O atoms of 1,4‐bdc dianions within different α‐polonium nets.