Hydrothermal synthesis, crystal structures, and properties of two Co(II) complexes based on 4-bromoisophthalic acid and N-donor ligands

Two new Co(II) complexes, [Co₂(H₂O)(Bipy)₂(Bript)₂] _n (I) and [Co(H₂O)(Phen)(Bript)] · H₂O (II), where H₂Bript = 4-bromoisophthalic acid, Bipy = 2,2??-bipyridine, and Phen = 1,10-phenanthroline, have been synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. Complex I has binuclear units in which two Co²⁺ ions are bridged by two carboxylate groups and a coordinaiod-water molecule, and the binuclear units are connected by Bript to generate a 1D helical chain. These 1D helical chains are further linked by ????? stacking interactions to form a 3D supramolecular network, while complex II has a 2D layer motif. In I and II, there exists extensive hydrogen bonding interactions. The thermal behavior of the two corresponding complexes have briefly been investigated.     

Hydrothermal synthesis, crystal structure, and properties of two novel binuclear complexes based on Zaltoprofen and 2,2′-bipyridine ligands

Two novel binuclear metal-organic coordination complexes [M₂(Zaltoprofen)₂(Bipy)₂] [M = Cd (I), Zn (II); Zaltoprofen = 5-(1-carboxyethyl)-2-(phenylthio)phenylacetic acid, Bipy = 2,2′-bipyridine) have been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction, elemental analysis, IR and electronic spectroscopy, powder X-ray diffraction, and fluorescent properties. Complexes I, II crystallize isomorphously in the monoclinic space group P2₁/c. Structural analysis shows that the M(II) atom of I and II is coordinated with four oxygen atoms from the carboxyl group of the Zaltoprofen together with two nitrogen atoms from the Bipy. The 3D structures of the complexes are stabilized by π-π stacking interactions.     

Yttrium complexes with N-donor ligands

Compounds [HBipy][Y(NCS)₄(Bipy)₂] · H₂O (I), [HPhen][Y(NCS)₄(Phen)₂] (II), and [Y(Nic)₃(H₂O)₂]₂ (III), where Bipy is 2,2′-bipyridine and Phen is 1,10-phenanthroline, are synthesized and structurally characterized by X-ray diffraction analyses (CIF files CCDC 984621, 984622, and 934971, respectively). In the anionic complexes, the coordination polyhedron of sodium is formed by eight nitrogen atoms, four of which are provided by the acido ligands and four others are given by two molecules of the N-heterocycle. In compounds I and II, the protonated and coordinated diimines together participate in stacking interactions.     

Manganese(II) and copper(II) complexes based on pentafluorobenzoate: interaction of fluorine in solid state

The synthesis and characterization of Mn(II) and Cu(II) complexes with the general formula [Mn(Phen)₂(Pfbz)₂](Hpfbz) (I) and [Cu₂(Bipy)₂(Pfbz)₄] (II) (Phen = 1,10-phenanthroline, Bipy = 2,2′-bipyridine, Pfbz = pentafluorobenzoate) are reported. I crystallizes in triclinic crystal system, space group {tiP}1 with a = 9.755(1), b = 11.302(1), c = 20.064(2) Å, α = 95.799(2)°, β = 90.176(2)°, γ = 113.993(2)°, and Z = 2. Complex II crystallizes in triclinic crystal system, space group P1 with a = 9.661(1), b = 9.951(1), c = 12.891(1) Å, α = 102.943(2)°, β = 98.972(2)°, γ = 96.746(2)°, and Z = 1. Of particular interest, intricate C-H…F and F…F interactions in the two crystals play important role in the formation of three dimensional supramolecular networks. F(lp)…π (lp = lone pair) interaction is recognized in the solid-state structure of II.     

Dipyridyl-type ligand-directed assembly of three cobalt(II) coordinated polymers based on carboxyphenylpropionate

A series of Co(II)-H₂Cpp coordination polymers incorporating different auxiliary ligands, [Co(Cpp)(Phen)(H₂O)] (I), {[Co(Bipy)(H₂O)₄](Cpp)} _n (II), and [Co(Cpp)(Bds)(H₂O)] _n (III) (H₂Cpp = 3-(4-carboxyphenyl)propionic acid, Phen = 1,10-phenanthroline, Bipy = 4,4′-bipyridyl, and Bds = 4,4′-bipyridyl sulfide), were synthesized by the hydrothermal reaction and characterized by single crystal X-ray diffraction, elemental analysis, IR, and TG. Three complexes display from 0D to 1D different structural features under the regulation of distinguishing dipyridyl-type coligands. Complex I possesses a binuclear Co(II) motif constructed by H₂Cpp and Phen, which further developing a zipper-like 2D layer via H-bonded and π-π stacking interactions. Complex II displays straight Bipy-bridging 1D chain, and further forming a 3D supramolecular structure by hydrogen-bonded interactions. Complex III exhibits 1D double-chain collectively jointed by Cpp and Bds, which further interlinked into a 3D supramolecular architecture by H-bonded interactions.     

Three one-dimensional chains with bulky backbone carboxylate ligands: Syntheses,crystal structures,and luminescent properties

To explore the influence of bulky backbone on complexes, three Co(II) and Zn(II) complexes with phenanthrene-9-carboxylate (L¹), 9H-fluorene-9-carboxylate (L²) or biphenyl-4-carboxylate (L³) together with incorporating auxiliary bridging ligad 4,4′-bipyridine (4Bipy), were synthesized and characterized: [Co(L¹)₂(4Bipy)(H₂O)₂]_∞ (I), [Zn(L²)₂(4Bipy)_0.5(4Bipy)_0.5]_∞ (II), and [Zn₃(L³)₄(4Bipy)_0.5(4Bipy)_0.5(4Bipy)_0.5(OH)₂]_∞ (III). X-ray single-crystal diffraction analyses show that complexes I–III both assume one-dimensional (1D) structures by incorporating the bridging 4Bipy (CIF file CCDC nos. 942729 (I), 942727 (II), and 942733 III). In I, mononuclear six-coordinated Co²⁺ ions are linked into a 1D linear chain by 4Bipy. While in II, mononuclear four-coordinated Zn²⁺ ions are linked into a 1D zigzag chain by 4Bipy. But in III, because of the existence of OH^?, hexanuclear Zn(II) can be regarded as a node, then bridge adjacent hexanuclear Zn(II) nodes by almost parallelled three 4Bipy ligands into a 1D linear chain. Finally the 1D chains of I–III are further assembled into an overall three-dimensional (3D) framework via intermolecular H-bonding, π…π stacking, and/or C-H…π supramolecular interactions, respectively. The results indicate that, besides different metal ions Co²⁺ and Zn²⁺ or OH^? anions, the steric hindrance of backbone ligands play an important role in the formation of I–III. Moreover, the luminescent properties of corresponding ligands and their complexes were briefly investigated.     

Mixed-ligand complexes based on asymmetric gadolinium β-diketonates: Synthesis, crystal structure, and theoretical modeling

Mixed-ligand complexes of asymmetric gadolinium β-diketonates with 2,2′-bipyridyl (Bipy)—[Gd(Pa)₃(Bipy)] (HPa is pivaloylacetone) (I) and [Gd(Pta)₃(Bipy)] (HPta is pivaloyltrifluoroacetone) (II)-have been obtained by direct interaction of initial reagents and their structures have been studied by X-ray crystallography. Crystals of I are monoclinic: a = 9.536(1) Å, b = 15.037(1) Å, c = 13.280(1) Å, β = 109.56(1)°, V = 1798.7(3) ų, Z = 2, space group P2₁. Crystals of II are triclinic: a = 9.6696(17) Å, b = 12.1348(9) Å, c = 18.243(3) Å, α = 100.257(12)°, β = 103.997(2)°, γ = 101.438(11)°, V = 1977.4(5), Z = 2, space group P $\bar 1$ . The coordination polyhedron of the central gadolinium atom in I and II is a distorted square antiprism formed by six oxygen atoms of the three β-diketonate ligands (av. Gd-O, 2.35(2) and 2.351(5) Å in I and II, respectively) and two nitrogen atoms of the Bipy ligand (av. Gd-N, 2.47(2) and 2.584(7) Å in I and II, respectively). Although the molecular structures of these complexes are similar, they have different crystal packings. In II, the planes of the Bipy ligands of neighboring molecules related by an inversion center are bound by stacking interaction (the distance between the Bipy planes is 3.45 Å). The structure and properties of these mixed-ligand complexes have been discussed based on the results of quantum-chemical density functional theory calculations (DFT/B3PW91). The nature of the substituents in the β-diketonate ligand has an effect on the structure and properties of the complexes. The correlation between the Gd-Dik and Gd (Dik)₃-Bipy bond energies has been studied.     

Design and synthesis of two-dimensional pillared MOF layers by connecting infinite one-dimensional chains via 4,4′-bipyridine

Two novel metal-organic frameworks, [Cd(Bna)(DMF)₂(H₂O)₂] _n · nDMF (I) (Bna = 2,2′-dihydroxy-l,l′-dinaphthyl-3,3′-dicarboxylate) and [Cd(Bna)(Bipy)(DMF)₂] _n (II) (Bipy = 4,4′-bipyridine) have been synthesized under mild conditions and structurally characterized. Crystal structural analyses reveal that complex I adots a 1D spiral structure with DMF guest molecules in the spiral by hydrogen bondings. Complex II is constructed by -Cd-Bna-Cd- zigzag chains, which are further connected by Bipy into a 2D sheet. X-ray powder diffraction and thermogravimetric analyses for I and II show that they are highly themally stable in the solid state.     

A new 2D Mn(II) coordination polymer constructed from carboxylate and N-donor coligand: Synthesis,structure, and magnetism

A new complexes, namely, {[Mn₂(L)₂(Bipy)₂] · H₂O} _n (I) (H₂L = diphenic acid, Bipy = 4,4′-bipyridine) has been synthesized and structurally characterized by single-crystal diffraction analysis. In I, the two syn, anti-carboxylate groups in L bridge Mn(II) forming a one-dimensional chain, which is further connected by Bipy into 2D double layer. Magnetic study reveals the overall antiferromagnetic interaction between neighboring Mn²⁺ ions in compound I.     

Hydrothermal synthesis, crystal structure, and photoluminescence of Pb(II) and Mn(II) coordination polymers based on imidazo[4,5-f][1,10]phenanthroline

Two new coordination polymers, [Pb(IDPT)₂(NO₃)₂] (I) and [Mn(IDPT)(SO₄)(H₂O)₂] (II) (IDPT = imidazo[4,5-f][1,10]phenanthroline), were synthesized by hydrothermal method and characterized by elemental analysis and single-crystal X-ray diffraction technique. The results reveal that the complex I belongs to monoclinic crystal system, space group C2/c and complex II belongs to monoclinic crystal system, P2₁/c space group. The cell parameters are: a = 19.1970(13), b = 7.3875(5), c = 17.3825(12) Å, β = 100.47(10)°, V = 2424.0(3) ų, Z = 4, F(000) = 1488 for I; a = 10.9135(6), b = 7.0230(4), c = 19.7034(10) Å, β = 99.32(10)°, V = 1490.25(14) ų, Z = 4, F(000) = 828 for II. In the structure of complex I, the metal center Pb(II) is six-coordinated, displays an octahedral geometry. Each molecule is further connected with neighboring one via π-π interactions into 1D chain. In complex II, Mn(II) is six-coordinated to form a distorted octahedral geometry. Compound II displays 1D supramolecular chain formed through hydrogen bonds. Additionally, the fluorescent properties for the complexes were investigated. Complexes I and II exhibit strong photoluminescence with emission maximum at 583 and 529 nm at room temperature.     

Two new oxamidato-bridged CuII-CuII complexes: Synthesis, structure, spectra, and cyclic voltammetry studies

New oxamido-bridged binuclear Cu^II-Cu^II complexes, [Cu(Oxen)Cu(Bipy)₂](ClO₄)₂ (I) and [Cu(Oxen)Cu(4,4??-Bipy)₂(H₂O)₂](ClO₄)₂ (II) (Oxen is N,N??-bis(2-aminoethyl)oxamide dianion, Bipy = 2,2??-bipyridine, 4,4??-Bipy = 4,4??-bipyridine), have been constructed and structurally characterized by X-ray crystallography. In these two complexes, each Cu²⁺ ion is located in a slightly distorted square-pyramidal environment. Complex I is extended to two-dimensional by face-to-face ??-??-stacking with a distance of 3.648 II is raised to one-dimensional by face-to-face ??-??-stacking and intermolecular H-bonding interaction with distances of 3.651 and 2.767 I is also investigated.     

anti-syn and anti-anti coordination of the bridging CO 3 2− group in [Cu2(Phen)4(μ-CO3)]B10H10 binuclear complexes: Synthesis, structure, and magnetic properties

A redox reaction that occurs in the [Cu₂B₁₀H₁₀]/Phen system in CH₃CN/DMSO and CH₃CN/DMF in air yields a Cu(II) binuclear complex, [(Phen)₂Cu(CO₃)Cu(Phen)₂]²⁺. The [Cu₂(Phen)₄(μ-CO₃)]B₁₀H₁₀ · 2.5DMSO · 2H₂O (I) and [Cu₂(Phen)₄(μ-CO₃)]B₁₀H₁₀ · 4DMF (II) compounds have been isolated and studied by X-ray crystallography at 150 K and EPR at 295 K. Their magnetic properties have been studied in the range 300–2 K. In the cations of both compounds, the bridging CO ₃ ^2? group is bidentately coordinated to two Cu atoms. The cations in I and II have different spatial orientations of the Cu-O bonds: anti-syn and anti-anti, respectively. Compound I has weak magnetic interactions caused by a short Cu…Cu distance (4.441 Å) in the dimer. No exchange coupling is observed in II.     

Synthesis and crystal structure of the Ag(I) complex with a cyclic β-diketone, 2-(diphenylacetyl)indan-1,3-dione (L), and the HL molecule

An Ag(I) complex with HL (I), AgL (AgC₂₃H₁₅O₃, II), has been synthesized. Compounds I and II have been studied by X-ray diffraction. The crystals are monoclinic, I: space group P2₁/n, a = 10.459(2) Å, b = 12.354(2) Å, c = 13.390(3) Å, β = 96.67(3)°, Z = 4; II: space group P2₁/c, a = 10.764(2) Å, b = 10.683(2) Å, c = 15.939(3) Å, β = 101.57(3)°, Z = 4. The structural units of the crystal of I are neutral molecules with intramolecular hydrogen bonds. In structure II, the Ag₂O₆ dimeric groups and the ligands form infinite openwork layers perpendicular to the x axis and containing cavities. The layers are penetrated by channels with an oblong cross section. In the crystal of II, all intermolecular distances exceed the sums of the van der Waals radii of the corresponding atoms.     

Crystal structures and luminescence of a series of cadmium(II) complexes based on isophorone derivative containing imidazolyl

Three new complexes, [CdL₂(CH₃COO)₂(H₂O)₂] (I), CdL₂Br₂ (II), CdL₂I₂ (III), have been successfully synthesized by self-assembly of corresponding metal salts with (E)-2-(3-(4-(1H-imidazole-1-yl)styryl)-5,5-dimethylcyclohex-2-enylidene)malononitrile (L). The structures of the complexes were determined by single crystal X-ray diffraction analysis (CIF file CCDC nos. 957831 (I), 957792 (II), 957832 (III)). In complex I, central metal is six-coordinated and the crystal packing shows a 3D supramolecular framework. Complexes II and III display the similar 2D supramolecular structures in which the central metals are four-coordination. The luminescent properties were investigated.     

Syntheses,Structures, and Magnetic Properties of Two Mn(II) Coordination Polymers Based on 4-Fluorocinnamic Acid and 1,10-Phenanthroline

Two Mn(II) coordination polymers, {[Mn₃ (Pfca)₆(Phen)₂] · 2DMF} _n (I) and [Mn(Pfca)₂(Phen)(H₂O)] _n (II) (HPfca = 4-fluorocinnamic acid, Phen = 1,10-phenanthroline), were synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and singlecrystal X-ray diffraction (CIF files CCDC nos. 967513 (I), 1542972 (II)). Complex I crystallizes in the triclinic crystal system, space group Pī with a = 11.0821(11), b = 12.2632(12), c = 15.0288(15) Å, α = 87.3760(10)°, β = 88.4610(10)°, γ = 81.2220(10)°, V = 2016.0(3) Å3, ρ_c = 1.369 g/cm³, M _r = 1662.25, Z = 1, F(000) = 853, μ = 0.543 mm^–1, the final R = 0.0592 and wR = 0.1681 for 15498 observed reflections with I > 2σ(I). Complex II is of monoclinic system, space group P2₁/c with a = 18.0539(19), b = 8.5806(9), c = 18.758(2) Å, β = 116.5700(10)°, V = 2599.0(5) ų, ρ_c = 1.491 g/cm³, M _r = 583.44, Z = 4, F(000) = 1196, μ = 0.567 mm^–1, the final R = 0.0337 and wR = 0.0853 for 18139 observed reflections with I > 2σ(I). Complex I features linear Mn(II)-trinuclear units, which form 1D chain structure through F···F weak interactions, and complex II is 1D polymeric Mn(II)-chains. Antiferromagnetic coupling interactions exist within Mn(II)- carboxylate trinuclear in I (J =–0.40 cm^–1) and Mn(II)-carboxylate chain in II (J =–0.45 cm^–1).     

Tansition metal complexes with 2-(1-(carboxymethyl)-2-methyl-1H-benzimidazol-3-ium-3-yl)acetate (HL): Synthesis and crystal structure of [Co(L)2(H2O)4] · 6H2O and [Cu(L)2(H2O)2] · 4H2O

Transition metal complexes of 2-(1-(carboxymethyl)-2-methyl-1H-benzimidazol-3-ium-3-yl)acetate (HL), namely [Co(L)₂(H₂O)₄] · 6H₂O (I) and [Cu(L)₂(H₂O)₂] · 4H₂O (II), have been synthesized by a hydrothermal procedure and characterized by X-ray crystallography, CIF files CCDC nos. 1007524 (I), 1007525 (II). Both I and II are mononuclear molecules. In I, the Co²⁺ ion is in octahedral coordiantion environment and surrounded by four O atoms from water molecules and two carboxylate O atoms of two deprotonated ligand (L^?) occupied six culmination. While in II, the Cu²⁺ ion is located in a square-planar geometry, bounded to two aqua O atoms and two carboxylate O atoms from L^?.     

Synthesis and Structure of Different-Metal Different-Ligand Germanium(IV) and Cobalt(II) or Copper(II) Complexes with 1-Hydroxyethylidenediphosphonic Acid and 1,10-Phenanthroline

Different-metal different-ligand complexes [{Co(Phen)₃}₂{Co(Phen)(H₂O)₄}₂][{Ge(μ-OH)(μ- Hedp)}₆Cl₂] (I), [{Cu(Phen)₂(H₂O)}₂(HPhen)₂][Ge(μ-OH)(μ-Hedp)]₆ · 20H₂O (II) (H₄Hedp = 1-hydroxyethylidenediphosphonic acid, Phen = 1,10-phenanthroline) were synthesized and studied by X-ray diffraction. According to X-ray diffraction data (CIF files CCDC nos. 1573112 (I), 1573113 (II)), compounds I and II are cation–anion type complexes in which the anions are represented by {[Ge(μ-OH)(μ-Hedp)]⁶}^6– and, in the case of I, two additional Cl^– ions, while the cations are [Co(Phen)₃]²⁺, [Co(Phen)(H₂O)₄]²⁺ in I and [Cu(Phen)₂(H₂O)]²⁺, HPhen⁺ in II. In the crystals of compounds I and II, the cations, anions, and water molecules are combined by numerous intermolecular hydrogen bonds, giving rise to a 3D network.     

Heterometallic complexes of macrocyclic oxamide with polycarboxylates: Syntheses,crystal structures,and magnetic properties

Three complexes with the formula [Co(Ip)(CuL)(H₂O)₂] · H₂O (I), [Co(Ip)(NiL)(H₂O)₂] · H₂O (II), [Co(CuL)₂(Hbtc)(H₂O)] (III), (H₂Ip = m-isophthalic acid; H₂L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien; H₃Btc = 1,3,5-benzenetricarboxylic acid) were synthesized and structurally characterized by elemental analysis, IR and UV spectroscopy. Single-crystal X-ray analyses reveal that the complexes I and II contain neutral heterometallic binuclear CoM (for I and II, M = Cu, Ni, respectively) moieties, and complex III contains discrete neutral trinuclear CoCu₂ moieties. The structures of I–III consist of two-dimensional supramolecular architecture formed by strong O-H…O intermolecular hydrogen bonds. Furthermore, the magnetic properties of complex I were investigated and discussed in detail.     

Syntheses and luminescence of four supramolecular coordination complexes with flexible ligand

Four d ¹⁰-based complexes with chemical formulae {[Zn(L¹)₂(H₂O)₂(4,4′-Bipy)₂] (I), {[Zn₂(L¹)₄(Mi)] · 4H₂O} (II), {[Zn(L¹)₂(Phen)] · H₂O} (III) {[Cd(L¹)₂(Phen)] · 2H₂O} (IV) (HL¹ = p-hydroxy phenylacetic acid, 4,4′-Bipy = 4,4′-bipyridine, Phen = 1,10-phenanthroline, Mi = 1,4-bis(imidazol-1-yl)butane) have been synthesized and structurally characterized by single crystal X-ray diffraction (CIF files CCDC nos. 1047119 (I), 1047120 (II), 1047121 (III), 1047122 (IV)). The significant effect of assistant ligands and metal ions on assembly of I?IV has been demonstrated, which leads to the formation of distinct crystalline products. Complexes I?IV show various coordination motifs with different existing forms and coordination modes of the organic ligands. Furthermore, extend supramolecular networks are connected by secondary interactions such as hydrogen-bonding and aromatic stacking. The thermal stability and luminescent properties of the compounds were discussed in detail.     

Construction of 0D to 3D Copper(II) MOFs based on heterocyclic carboxylic acid: Synthesis,structures, cyclic voltammograms,and luminescent properties

The crystal structures of MOFs [Cu(PDA)(Phen)(H₂O)]₂ · 5H₂O (I) and [Cu(PZCA)₂(H₂O)₂] · 2H₂O (II) (H₂PDA = pyridine-2,6-dicarboxylic acid, Phen = 1,10-phenanthroline, HPZCA = pyrazine-2-carboxylic acid, H₂PZDA = pyrazine-2,3-carboxylic acid) have been prepared under hydrothermal conditions. These MOFs have been characterized by element analysis, single-crystal X-ray diffraction, thermogravimetric analyses and IR spectroscopy. 3D frameworks of MOFs I and II are fabricated from zero-dimensional (0D) motifs through hydrogen bonds and π-π interactions. In MOF II, the PZCA ligand comes from in situ decarboxylation of the part of pyrazine-2,3-dicarboxylic acid (H₂PZDA). Luminescent emissions bands of MOF I in methanol have been measured at room temperature and it displays selectivity to Zn²⁺, Cu²⁺, Pb²⁺, and Cd²⁺ ions. Cyclic voltammetry of MOFs I and II showed that the Cu(II/I) couple is irreversible.