Hydrothermal Syntheses and Structures of Lanthanide Coordination Polymers with 5-Aminoisophthalate and 1,10-Phenthroline

Abstract  

Two new lanthanide coordination polymers, [Ln₂(APA)₂(HAPA)₂(phen)₂] _n [Ln = Pr (1), Eu (2); H₂APA = 5-aminoisophthalic acid, phen = 1,10-Phenanthroline] have been synthesized by hydrothermal method, and characterized by single crystal X-ray diffraction, elemental analysis and IR spectra. Crystallographic data show that complexes 1 and 2 both crystallize in a triclinic system, space group P[`1] P\bar{1} . The titled compounds own 2-D herringbone structures which are further constructed to form 3-D supramolecular structures by N–H···O and O–H···O hydrogen bondings. The thermogravimetric analyses were carried out to examine the thermal stability of the title complexes. And the photoluminescence property of 2 was investigated.     

Synthesis and Crystal Structure of the Heteronuclear Decavanadates Complex: [Fe(phen)<Subscript>3</Subscript>]<Subscript>2</Subscript>·[V<Subscript>10</Subscript>O<Subscript>28</Subscript>]·15H<Subscript>2</Subscript>O

Abstract  

A new decavanadate metal complex [Fe(phen)₃]₂·[V₁₀O₂₈]·15H₂O (phen = 1,10-phenanthroline) has been synthesized from a hydrothermal reaction and the crystal structure has been determined by means of single-crystal X-ray diffraction. The crystal structure analysis reveals that the polyoxoanions are decorated with the [Fe(phen)₃]³⁺ cations, and that the water molecules play the bridge role on the packing modes. They are further contacted to form supramolecular networks through extensive hydrogen bonding.     

Two Isostructural Complexes Constructed from Mixed Ligands of Dipyrido[3,2-d:2′,3′-f]quinoxaline and Phthalate with Novel Oxygen Clusters

Abstract Two isostructural dinuclear complexes [M₂(Dpq)₂(phth)₂(H₂O)₄] · 2H₂O [M = Zn(1), Ni(2), Dpq = dipyrido[3,2-d:2′,3′-f]quinoxaline, phth = phthalate] have been synthesized and characterized. Crystal data: (1), Mr = 1031.55, monoclinic, C2/c, a = 27.7948(11), b = 10.5196(4), c = 15.0390(5) ?, β = 110.818(1), Z = 4, V = 4110.2 ?³, R ₁ = 0.0277, wR ₂ = 0.0718 [I > 2σ(I)]; (2), Mr = 1018.19, monoclinic, C2/c, a = 27.675(4), b = 10.3601(15), c = 15.082(2) ?, β = 110.954(2), Z = 4, V = 4038.3 ?³, R ₁ = 0.0248, wR ₂ = 0.0668 [I > 2σ(I)]. The dinuclear units are connected into 2-D supramolecular net through O–H···O hydrogen bonding. Moreover, the 2-D networks are ultimately packed into a 3-D supramolecular structure via interlayer π···π stacking interaction between the aromatic rings of Dpq ligands. Furthermore, the photoluminescence property of compound 1 is also studied. Graphical Abstract Two isostructural dinuclear complexes [M₂(Dpq)₂(phth)₂(H₂O)₄] · 2H₂O [M = Zn(1), Ni(2), Dpq = dipyrido[3,2-d:2′,3′-f]quinoxaline, phth = phthalate] have been synthesized, and the structure study reveals that each dinuclear complex is connected with six other dinuclear units through the O–H···O hydrogen bonding to form 2-D supramolecular networks.      

Synthesis and Crystal Structure of a Novel Double-Chain Coordination Polymer [Zn<Subscript>2</Subscript>(bipy)<Subscript>2</Subscript>(btec)(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>]<Subscript>n</Subscript> (bipy = 2,2′-bipyridine; btec = 1,2,4,5-benzenetetracarboxylate)

Abstract  A novel aromatic polycarboxylate polymer, [Zn₂(bipy)₂(btec)(H₂O)₂]_n (1), has been synthesized and structurally characterized by the single crystal X-ray diffraction. Compound 1 belongs to the triclinic crystal system, space group P-1; a = 7.7449(6) ?, b = 8.9286(8) ?, c = 10.7422(8) ?, α = 80.95(1)°, β = 70.21(1)°, γ = 78.14(1)°, V = 680.93(10) ?³, Z = 2. The coordination geometry of Zn(II) atom is distorted trigonal bipyramidal with two nitrogen atoms of one 2,2′-bipy group, two oxygen atoms from two different btec ligands, and one water. The 16-membered rings are alternately arranged forming an infinite 1-D double-chain structure. A 3-D network was constructed by interlayer C···H–O, O···H–O hydrogen bonds and π–π stacking interactions. Compound 1 exhibits fluorescence at room temperature in the solid state. Graphical Abstract  A 1-D double-chain aromatic polycarboxylate polymer, [Zn₂(bipy)₂(btec)(H₂O)₂]_n (1), has been synthesized and structurally characterized by the single crystal X-ray diffraction. A 3-D network was constructed by intermolecular C···H–O, O···H–O hydrogen bonds and π–π stacking interactions. Compound 1 exhibits fluorescence at room temperature in the solid state.      

Different complexation behavior of a proton transfer compound obtained from 1,10‐phenanthroline and pyridine‐2,6‐dicarboxylic acid with Sn(IV), Sb(III) and Tl(I)

The different complexation methods of a proton transfer compound, (phenH)₂(pydc) (phen=1,10‐phenanthroline; pydcH₂= pyridine‐2,6‐dicarboxylic acid), are discussed and formation of [Sn(pydc)(phen)(OH)₂]·3H₂O ( 1 ), {[Sb(pydc)(phen)]₂O}·2DMSO·4H₂O( 2 ) and [(Tl(pydcH)]_n ( 3 ) complexes are reported. The characterization was performed using IR spectroscopy and X‐ray diffraction. The structures of Sn(IV) and Sb(III) complexes show that both cationic and anionic fragments of the starting proton transfer compound have been involved in the complexation. Whereas the structure of Tl(I) complex demonstrates that only the anionic fragment of (phenH)₂(pydc) is contributed to the complexation. The complexes 1‐3 show a variety of structural features including mononuclear, binuclear and polymeric structures. In compounds ( 1 ), ( 2 ) and ( 3 ) a large number of hydrogen bonds are observed. These interactions play an important role in the formation and stabilization of supramolecular systems in the crystal lattices. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Non-Covalent Interactions in a Nickel(II) Complex with Benzilate and 1,10-Phenanthroline

Abstract  

A new mixed-ligand nickel(II) coordination compound [Ni(bz)₂(phen)₂] (1) (bz = benzilate and phen = 1,10-phenanthroline) has been synthesized by refluxing nickel(II) acetate with benzilic acid and 1,10-phenantholine. Compound 1 has been characterized by elemental analysis, IR and electronic absorption spectroscopy, magnetic measurements, thermogravimetric analysis and single-crystal X-ray diffraction The crystal of 1 belongs to monoclinic crystal system, space group C2/c and its unit cell parameters are a = 25.881(3), b = 11.1728(15), c = 17.609(2) ? and β = 124.104(3)°. The effect of non-covalent interactions, such as π···π and C–H···π, on the 3D supramolecular organization of this molecular complex is analyzed.     

Crystal growth,structure and characterization of diglycine zinc dipicrate: Centrosymmetric crystal exhibiting second harmonic generation efficiency

A new cadmium coordination polymer, formulated as [Cd(L)(phen)]_n, were prepared by hydrothermal reactions based on 3,4-dibromothiophene-2,5-dicarboxylic acid (H₂L) and 1,10-phenanthroline (phen) mixed organic linkers. In the complex, adjacent Cd²⁺ ions are linked by L^2? anions to form a one-dimensional (1D) [CdL]_n chain with [Cd₂(COO)₂] as the secondary building unit (SBU). These adjacent chains are further stacked together by direct C?Br···Br halogen bonds interactions, generating a two-dimensional (2D) supramolecular structure. From the viewpoint of topology, the 2D supramolecular network can be rationalized to a 3,4-connected 3,4L13 net with {4.6²}₂{4².6².8²} topology.     

Two d10 Coordination Complexes Based on the Substitutional Aromatic Multicarboxylate and N-Donor Co-Ligands: Syntheses,Structures, and Properties

Two new coordination complexes, formulated as [Cd₂(3-NPA)(phen)₄(H₂O)₂]₂ (1) and [Zn(3-NPA)(phen)(H₂O)]_n (2) (3-NPAH₂ = 3-nitrophthalic acid, phen = 1,10-phenanthroline) have been synthesized by hydrothermal reactions of the rigid neutral ligand phen with metal ions in the presence of 3-NPAH. X-ray analysis shows that complex 1 is a 0D dinuclear structure that is arranged to form a 3D supramolecular framework through hydrogen bonds and π–π stacking interactions. In polymer 2, the 3-NPA^2? anions coordinate the Cd(II) ions in a tridentate mode to form a 1D infinite chain structure, which is connected by the hydrogen bonds and π–π stacking interactions resulting in a 3D supramolecular architecture. In addition, the two complexes were characterized by infrared spectroscopy, elemental analysis, luminescent properties, thermo gravimetric analysis, and powder X-ray diffraction (PXRD).     

Synthesis,Structure and Electrochemical Property of a New Copper(II) Complex Based on Benzene-1,2,4,5-tetracarboxylate and 2,5-Bis(3-pyridyl)-1,3,4-oxadiazole Ligands

Abstract  

A new three-dimensional (3-D) supramolecular complex, [Cu₂(btec)(bpo)₂(H₂O)₂]·8H₂O (1), has been synthesized by hydrothermal reaction with the mixed ligands benzene-1,2,4,5-tetracarboxylate (btec) and bent dipyridyl based ligand 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (bpo), and structurally characterized by elemental analysis, IR, TG, powder-XRD and single-crystal X-ray diffraction analysis. The results reveal that each Cu(II) ion is bridged by two different ligands (btec and bpo) to form a 2-D polymer layer in complex 1. The adjacent layers are further linked by 1-D H-bonded water chains simultaneously containing (H₂O)₆ rings and (H₂O)₈ rings to form a 3-D supramolecular framework. Moreover, the electrochemical behavior of complex 1 bulk-modified carbon paste electrode (1-CPE) has been reported.     

Synthesis,Crystal Structure and Characterizations of New 3,4,7,8-Tetrachloro-1,10-Phenanthroline Zn(II) Complex

Abstract  

A novel 3,4,7,8-tetrachloro-1,10-phenanthroline (Cl₄phen) Zn(II) complex has been synthesized. The complex, [Zn(Cl₄phen)₂(H₂O)₂](NO₃)₂·CH₃CH₂OH (1), has been identified and characterized by single crystal X-ray diffraction, elemental analysis, FT-IR, thermogravimetric analysis and photoluminescence studies. Single crystal X-ray diffraction analysis reveals that complex (1) belongs to the monoclinic system, space group P2(1)/c, a = 10.061(2) Å, b = 18.924(4) Å, c = 18.189(4) Å, β = 100.94(3)°, and Z = 4. Complex (1) consists of cationic species [Zn(Cl₄phen)₂(H₂O)₂]²⁺, NO₃ ⁻ and CH₃CH₂OH. The zinc atom displays a distorted cis-N₄O₂ octahedral geometry. Via extended Zn–O–H···O–N–O···H–O–Zn bridge, every mononuclear unit is linked with other ones to form one-dimensional (1D) infinite chain of hydrogen bond system. Three-dimensional (3D) polymeric network arrangement was built via weak C–H···O and π-stacking interactions between Cl₄phen moieties. A solvent-dependency effect of complex (1) was observed in spectroscopic properties.     

Synthesis,Crystal Structure and Optical Properties of a Three-Dimensional Supramolecule Assembled by a Dinuclear Neodymium Cluster

Abstract  

The reaction of isonicotinic acid (IN), sodium hydroxide, 1,10-phenanthroline (phen) and neodymium nitrate leads to the formation of a novel complex [Nd(phen)(IN)₂(NO₃)(H₂O)₂]₂ 1, which has been characterized by single crystal X-ray diffraction analysis: monoclinic, space group C2/c, with a = 24.93(2) Å, b = 9.452(3) Å, c = 21.406(5) Å, β = 97.87(2)°, and Z = 4. Complex 1 consists of a centrosymmetric dinclear molecule, and neodymium atoms are bridged by two carboxyl groups of two IN ligands. The dinuclear clusters of 1 are connected each other into a three-dimensional (3D) supramolecular framework, which is stabilized by O–H···O, O–H···N hydrogen bonds as well as π–π stacking interactions. Its electronic absorption and luminescence properties have also been investigated.     

Construction of one new two-dimensional Zn(II) coordination polymer based on thiophene-2,5-dicarboxylate and bis(imidazole) mixed ligand

Under hydrothermal conditions, a new two-dimensional (2D) zinc coordination polymer, [Zn(tdc)(bimm)]_n, was synthesized based on thiophene-2,5-dicarboxylic acid (H₂tdc) and 1,2-bis(imidazol-1′-yl)methane (bimm) mixed ligands. Single crystal X-ray structural analysis shows adjacent Zn²⁺ ions are connected by tdc^2? anions to form a one-dimensional (1D) [ZnL]_n chain in the complex. Then flexible bimm ligands expand 1D chains into a 2D layer by linking neighboring Zn²⁺ ions. These adjacent layers are further stacked together by direct C?H···π supramolecular interactions, generating a double-layer 2D supramolecular structure. In topology, the 2D lay could be rationalized to a uninodal 4-connected non-interpenetrated sql net with {4⁴.6²} topology. In addition, solid state properties such as thermogravimetric analysis and luminescence were also investigated.     

Two Ag(I)-Containing Supramolecular Coordination Polymers Constructed from the Multidentate N-donor Ligand 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole Based on Hydrogen-Bonding and π–π Interactions: Syntheses,Crystal Structures,Optical Band Gaps and Luminescent Properties

Two Ag(I)-based coordination polymers, namely [Ag₂(3,3′-tmbpt)(o-Hbdc)₂]·H₂O (1) and [Ag₈(3,3′-tmbpt)₄(1,2,4-Hbtc)₄(H₂O)] (2) (3,3′-tmbpt?=?1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole, o-H₂bdc?=?1,2-benzenedicarboxylic acid and 1,2,4-H₃btc?=?1,2,4-benzenetricarboxylic acid), have been synthesized. Single-crystal X-ray diffraction analyses, elemental analyses, infrared spectra, powder X-ray diffraction analyses and thermogravimetric analyses have been carried out to characterize the structures of 1 and 2. Compound 1 shows a (3,4)-connected 2D layered structure with a Schläfli symbol of (4²·6)(4²·6³·8). The intermolecular O–H···O hydrogen-bonding interactions extend the 2D layer into a 3D supramolecular architecture. Compound 2 exhibits a (3,3)-connected double-layered structure with a Schläfli symbol of (4·8·10)₂(8²·10)₂. The intermolecular C–H···O hydrogen-bonding interactions link the double-layers to form a 3D supramolecular architecture. Moreover, there are intramolecular and intermolecular π–π interactions in 1 and 2, which stabilize the whole 3D supramolecular architectures. The band gaps of 1 and 2 are 3.19 and 3.09 eV, respectively, indicating the potential of 1 and 2 as semiconductive materials with wide band gaps. Moreover, 1 and 2 emit intense blue-green light, which may be potential photoactive materials.

Graphic Abstract

Two Ag(I)-based 3D supramolecular coordination polymers constructed from a multidentate N-donor ligand and two aromatic polycarboxylate anions via hydrogen-bonding and π–π interactions have been synthesized and characterized. The band gaps and photoluminescent properties of the compounds have been studied.

     

Synthesis, Crystal Structure of a New Co(II) Complex with Pyrazine-2,3,5,6-tetracarboxylic Acid

Abstract A new complex [Co(H₂pztc)(bpy)H₂O] (H₄pztc = pyrazine-2,3,5,6-tetracarboxylic acid, bpy = 2,2′-bipyridine) has been synthesized by hydrothermal reactions of Co(NO₃)₂ · 6H₂O with H₄pztc and bpy and characterized by IR and X-ray diffraction single crystal structure analysis. It belongs to monoclinic system, P2₁/c space group with a = 13.454(2) ?, b = 12.939(2) ?, c = 11.4993(19) ?, α = 90°, β = 111.640(3)°, γ = 90°. This complex is assembled into 3D supramolecular architecture by hydrogen bonds (O–H···O, C–H···O). Index Abstract A new complex of cobalt(II) with pyrazine-2,3,5,6-tetracarboxylic acid and 2,2′-bipyridine is assembled by intermolecular hydrogen bonds forming 2D layer and 3D supramolecular network.      

Synthesis,Structure, and Fluorescence of a Novel Cadmium Compound

A novel cadmium compound, [(CdI₃)₂(μ₂-I)]₂(Me₂-4,4'-H₂bipy)₃ (1) (Me = methyl; 4,4'-bipy = 4,4'-bipyridine) with the Me₂-4,4'-H₂bipy moiety generated in situ, has been prepared through a solvothermal reaction and structurally characterized by X-ray single crystal diffraction analysis. Compound 1 is characterized by an isolated structural motif, consisting of [(CdI₃)₂(μ₂-I)]^3– anions and Me₂-4,4'-H₂bipy²⁺ cations. The [(CdI₃)₂(μ₂-I)]^3– anions and Me₂-4,4'-H₂bipy²⁺ cations interconnect together via C–H···I hydrogen-bonding interactions to complete a three-dimensional (3D) supramolecular network. Solid state fluorescent spectrum reveals an emission band in the violet region.     

Synthesis and supramolecular interactions involved in the crystal structure of (2,4,10,12-tetrabromo-6,7,14,15-tetrahydro-6, 14-thiacycloocta[1,2-b:5,6-b’]diquinoline)2·(1,1,2,2-tetrachloroethane) inclusion compound

The tetrahalo aryl inclusion host 2,4,10,12-tetrabromo-6,7,14,15-tetrahydro-6,14-thiacycloocta[1,2-b:5,6-b’]diquinoline 3 was re-synthesized to explore its ability to trap toxic polychlorinated hydrocarbons such as 1,1,2,2-tetrachloroethane (TCE) in the form of host–guest compound. Host 3 crystallizes from a fresh sample of TCE to form an inclusion compound of the formula (3)₂·(TCE) in triclinic system, space group P-1, with a = 7.7732(16) Å, b = 10.739(2) Å, c = 14.816(3) Å, α = 97.329(4)°, β = 98.619(4)°, γ = 103.359(4)°, V = 1172.7(4) ų, and Z = 2. The X-ray crystal structure of the (3)₂·(1,1,2,2-TCE) is described and analyzed in terms of crystal engineering and supramolecular chemistry. The hosts assemble by means of different types of packing motifs. The included TCE molecules are enclosed within host molecular pens. Novel halogen···halogen intermolecular interactions as well as other non-covalent intermolecular interactions involved in the crystal structure are presented and proved to play an important role in linking these host–host, host–guest, and guest–guest building blocks.     

Encapsulation Characteristics of Cavitand Type Tetrabromo-Functionalized Resorcin[4]arenes in the Crystal Structure

Single crystal X-ray diffraction analysis of upper rim functionalized tetrabromo-resorcin[4]arenes are presented and their guest encapsulation abilities are discussed. The Br-atoms either attached directly to resorcinarene rim or extended by methylene group (CH₂–Br). The substituents on the upper-rim plays an important role in the guest encapsulation characteristic of the resorcinarene cavity. In the crystal structure the host–guest supramolecular systems were stabilized by C–H?O, C–H?π and C?H···Br nonbonding interactions. The Hirshfeld surfaces analysis and the related 2D fingerprint plots provided qualitative and quantitative account of the various supramolecular non-bonding interactions present within the crystal.

Graphic Abstract

Guest encapsulation characteristic of tetrabromo-functionalized resorcin[4]arenes.

     

Synthesis,characterization and crystal structure of a 3‐D supramolecular Cu/Mn complex with pydc

A supramolecular compound, {[CuMn(pydc)₂(H₂O)₅]·2H₂O} ( 1 ) (pydc = pyridine‐2,6‐dicarboxylate dianion), has been synthesized and characterized by single‐crystal X‐ray diffraction. Single‐crystal X‐ray analysis reveals that it crystallizes in the triclinic space group P‐1, a = 8.4763(17) Å, b = 9.7715(19) Å, c = 13.909(3) Å, α =101.234(3)°, β =102.520(3)°, γ= 97.375(4)°. Two mixed‐metal ions exhibit similar coordinated geometries with octahedron. 1 possesses a 3‐D unusual supramolecular network featuring 1D water tape. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,crystal structure and photophysical studies on a ruthenium(II) carbonyl hydrido compound based on 2,2′‐bipyridyl‐5,5′‐dicarboxylic acid (H2bpdc)

A novel complex, namely [Ru^II(PPh₃)(CO)(H)(Hbpdc)]·2MeOH ( 1 ) (H₂bpdc = 2,2′‐bipyridyl‐5,5′‐dicarboxylic acid), has been synthesized from the reaction of H₂bpdc with [Ru^II(PPh₃)₃(CO)(H)₂] in methanol under mild condition and characterized by elemental analysis, IR spectrum, ESI mass spectrometry, and single crystal X‐ray diffraction. The structure shows that the complex crystallizes in the monoclinic space group P2₁/c with unit cell parameters a = 11.8984(13) Å, b = 16.5180(18) Å, c = 25.5322(19) Å, β = 115.302(4)°, V = 4536.6(8) ų, Z = 4. This compound features a 1‐D supramolecular chain constructed via hydrogen bonds. Its photophysical properties have been investigated in MeOH solution and in the solid state at room temperature.     

Hydrogen Bonding Patterns in 2,6-diamino-4-oxopyrimidinium Sulfosalicylate Monohydrate

The title compound, [C₄H₇N₄O⁺, C₇H₅O₆S^? . H₂O] contains one 2, 6-diamino-4-oxopyrimidinium cation, one sulfosalicylate anion and a water molecule. The crystal structure was determined by single crystal X-ray diffraction. This compound crystallized in the orthorhombic system; space group Pna2₁ with the unit cell parameters a = 13.402(3) Å, b = 16. 221(3) Å, c = 6.714(2) Å, V = 1459.6(6), Z = 4. The sulfonic acid group has protonated the aminopyrimidine moiety. The protonated N1 atom and N4 amino group are hydrogen bonded to the keto group (O1) of the neighbouring pyrimidine forming a six-membered ring with graph-set notation R₂ ¹(6) and a supramolecular chain along the c-axis. This supramolecular chain is further strengthened by one of the sulfonate oxygen atoms (O3), bridging the pyrimidines via hydrogen bonded rings, R₃ ²(10) involving N(3)–H(3)···O(3) and N(2)–H(2B)···O(3) hydrogen bonds. The other two oxygen atoms of the sulfonate groups are bridged by water molecules via O-H···O hydrogen bonds constituting a supramolecular chain. The water molecule also acts as hydrogen bond acceptor with respect to the carboxyl group.