Conformational Analysis of Eu(III)-(Ethylenedinitrilo)tetrakis(methylphosphonates) (EDTMP)

2008 ◽  
Vol 73 (11) ◽  
pp. 1437-1456 ◽  
Author(s):  
Lidia Smentek ◽  
B. Andes Hess
Keyword(s):  
Hydrogen Bonds ◽  
Dft Calculations ◽  
Metal Ion ◽  
Electrostatic Interactions ◽  
Electric Dipole Transition ◽  
Dipole Transition ◽  
Water Molecules ◽  
Qualitative Comparison ◽  
Lanthanide Ion ◽  
Positively Charged

The optimal geometries obtained from DFT calculations are presented for Eu(III)-EDTMP (the parent system) and cages associated with the water molecules and carbonate and hydroxide ions. The numerical results demonstrate the existence of two conformers of each cage, which might explain the observation of two spectroscopic lines previously assigned to the electric dipole transition 7F0 ↔ 5D0 of Eu3+. It is also found that the water molecules are associated with the chelate via hydrogen bonds with the oxygens of the phoshonate arms, while the carbonate and hydroxide ions are chelated with the lanthanide ion due to strong electrostatic interactions between the negatively charged oxygen atoms and positively charged metal ion. The analysis is illustrated by the qualitative comparison of the energies and is concluded with the relative stability of various chelates and energetically favorable, hypothetical reactions.

scholarly journals Cooperation/Competition between Halogen Bonds and Hydrogen Bonds in Complexes of 2,6-Diaminopyridines and X-CY3 (X = Cl, Br; Y = H, F)

Symmetry ◽  
2021 ◽  
Vol 13 (5) ◽  
pp. 766
Author(s):  
Barbara Bankiewicz ◽  
Marcin Palusiak
Keyword(s):  
Complex Formation ◽  
Hydrogen Bonds ◽  
Dft Calculations ◽  
Electrostatic Interactions ◽  
Dipole Moments ◽  
Main Role ◽  
Halogen Bonds ◽  
Topological Parameters ◽  
Leading Role ◽  
The Impact

The DFT calculations have been performed on a series of two-element complexes formed by substituted 2,6-diaminopyridine (R−PDA) and pyridine (R−Pyr) with X−CY3 molecules (where X = Cl, Br and Y = H, F). The primary aim of this study was to examine the intermolecular hydrogen and halogen bonds in the condition of their mutual coexistence. Symmetry/antisymmetry of the interrelation between three individual interactions is addressed. It appears that halogen bonds play the main role in the stabilization of the structures of the selected systems. However, the occurrence of one or two hydrogen bonds was associated with the favourable geometry of the complexes. Moreover, the impact of different substituent groups attached in the para position to the aromatic ring of the 2,6-diaminopyridine and pyridine on the character of the intermolecular hydrogen and halogen bonds was examined. The results indicate that the presence of electron-donating substituents strengthens the bonds. In turn, the presence of electron-withdrawing substituents reduces the strength of halogen bonds. Additionally, when hydrogen and halogen bonds lose their leading role in the complex formation, the nonspecific electrostatic interactions between dipole moments take their place. Analysis was based on geometric, energetic, and topological parameters of the studied systems.

scholarly journals Isotypic MnIIand FeIIbinuclear complexes of the ligand 5,6-bis(pyridin-2-yl)-pyrazine-2,3-dicarboxylic acid

2016 ◽  
Vol 72 (10) ◽  
pp. 1412-1416
Author(s):  
Monserrat Alfonso ◽  
Helen Stoeckli-Evans
Keyword(s):  
Hydrogen Bonds ◽  
Dicarboxylic Acid ◽  
Metal Ion ◽  
Three Dimensional ◽  
Water Molecules ◽  
Inversion Symmetry ◽  
Π Interactions ◽  
Metal Atoms ◽  
Hydrogen Bonded

The title isotypic complexes, bis[μ-5,6-bis(pyridin-2-yl)pyrazine-2,3-dicarboxylato]-κ4N1,O2,N6:O3;κ4O3:N1,O2,N6-bis[diaquamanganese(II)] tetrahydrate, [Mn2(C16H8N4O4)2(H2O)4]·4H2O, (I), and bis[μ-5,6-bis(pyridin-2-yl)pyrazine-2,3-dicarboxylato]-κ4N1,O2,N6:O3;κ4O3:N1,O2,N6-bis[diaquairon(II)] tetrahydrate, [Fe2(C16H8N4O4)2(H2O)4]·4H2O, (II), are, respectively, the manganese(II) and iron(II) complexes of the ligand 5,6-bis(pyridin-2-yl)-pyrazine-2,3-dicarboxylic acid. The complete molecule of each complex is generated by inversion symmetry. Each metal ion is coordinated by a pyrazine N atom, a pyridine N atom, two carboxylate O atoms, one of which is bridging, and two water O atoms. The metal atoms haveMN2O4coordination geometries and the complexes have a cage-like structure. In the crystals of both compounds, the complexes are linked by O—H...O and O—H...N hydrogen bonds involving the coordinating water molecules, forming chains along [100]. These chains are linked by O—H...O hydrogen bonds involving the non-coordinating water molecules, forming layers parallel to (011). The layers are linked by pairs of C—H...O hydrogen bonds and offset π–π interactions, so forming a hydrogen-bonded three-dimensional framework.

Binding of metal ions and water molecules to nucleic acid bases: the influence of water molecule coordination to a metal ion on water–nucleic acid base hydrogen bonds

2019 ◽  
Vol 75 (3) ◽  
pp. 301-309
Author(s):  
Jelena M. Andrić ◽  
Ivana M. Stanković ◽  
Snežana D. Zarić
Keyword(s):  
Nucleic Acid ◽  
Hydrogen Bonds ◽  
Nucleic Acids ◽  
Metal Ions ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
Metal Ion ◽  
Water Molecules ◽  
Nucleic Acid Bases ◽  
Coordinated Water

The interactions of nucleic acid bases with non-coordinated and coordinated water molecules were studied by analyzing data in the Protein Data Bank (PDB) and by quantum chemical calculations. The analysis of the data in the crystal structures from the PDB indicates that hydrogen bonds involving oxygen or nitrogen atoms of nucleic acid bases and water molecules are shorter when water is bonded to a metal ion. These results are in agreement with the quantum chemical calculations on geometries and interaction energies of hydrogen bonds; the calculations on model systems show that hydrogen bonds of nucleic acid bases with water bonded to a metal ion are stronger than hydrogen bonds with non-coordinated water. These calculated values are similar to the strength of hydrogen bonds between nucleic acid bases. The results presented in this paper may be relevant to understand the role of water molecules and metal ions in the process of replication and stabilization of nucleic acids and also to understand the possible toxicity of metal ion interactions with nucleic acids.

scholarly journals catena-Poly[[lithium-μ2-(dihydrogen pyrazine-2,3,5,6-tetracarboxylato)-κ6O2,N1,O6;O3,N4,O5-lithium-di-μ-aqua-κ4O:O] 2.5-hydrate]

2014 ◽  
Vol 70 (6) ◽  
pp. m234-m235 ◽  
Author(s):  
Wojciech Starosta ◽  
Janusz Leciejewicz
Keyword(s):  
Hydrogen Bonds ◽  
Metal Ion ◽  
Three Dimensional ◽  
Site Occupancy ◽  
Water Molecules ◽  
Site Symmetry ◽  
Orthorhombic Unit Cell ◽  
Trigonal Bipyramidal ◽  
Carboxylate Groups ◽  
A Site

The title coordination polymer, {[Li2(C8H2N2O8)(H2O)2]·2.5H2O}n, is built up from molecular ribbons propagating in thec-axis direction of the orthorhombic unit cell; the ligand bridges two Li+ions using both itsN,O,O′-bonding sites and adjacent Li+ions are bridged by pairs of water molecules. The coordination geometry of the metal ion is distorted trigonal bipyramidal, with the ligand O atoms in the axial sites. Two of the carboxylate groups of the ligand remain protonated and form short symmetric O—H...O hydrogen bonds. In the crystal, the ribbons interactviaa network of O—H...O hydrogen bonds in which coordinating water molecules act as donors and carboxylate O atoms within adjacent ribbons act as acceptors, giving rise to a three-dimensional framework. O—H...N interactions are also observed. The asymmetric unit contains quarter of the ligand and the complete ligand has 2/msymmetry; the Li+ion lies on a special position withm.. site symmetry. Both bridging water molecules havem2msite symmetry and both lattice water molecules havem.. site symmetry; one of the latter was modelled with a site occupancy of 0.25.

scholarly journals Crystal structures of two isotypic lanthanide(III) complexes: triaqua[2,6-diacetylpyridine bis(benzoylhydrazone)]methanollanthanide(III) trichloride methanol disolvates (Ln III = Tb and Dy)

2018 ◽  
Vol 74 (4) ◽  
pp. 535-538 ◽  
Author(s):  
Chihiro Kachi-Terajima ◽  
Norihisa Kimura
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Lanthanide Complexes ◽  
Three Dimensional ◽  
Lanthanide Ions ◽  
Water Molecules ◽  
Coordination Geometry ◽  
Lanthanide Ion ◽  
Π Interactions ◽  
Coordinated Water

The title lanthanide complexes, [Ln(DAPBH2)(CH3OH)(H2O)3]Cl3·2CH3OH [Ln III = Tb and Dy; DAPBH2 = 2,6-diacetylpyridine bis(benzoylhydrazone), C23H21N5O2], are isotypic. The central lanthanide ions are nine-coordinate, being ligated by three N and two O atoms from the pentadentate DAPBH2 ligand, and four O atoms from the coordinated methanol molecule and three coordinated water molecules. The coordination geometry of the lanthanide ion is a distorted capped square antiprism. In the crystals, the various components are linked by O—H...Cl, N—H...Cl and O—H...O hydrogen bonds, forming three-dimensional supramolecular frameworks. Within the frameworks, there are C—H...Cl and C—H...O hydrogen bonds and offset π–π interactions (intercentroid distance ca 3.81 Å).

Synthese und Kristallstrukturen der Bis(oxalato)metallate trans-K3[RhCl2(C2O4)2]· 4 H2O und cis -K3[IrCl2(C2O4)2]· H2O / Synthesis and Crystal Structures of the Bis(oxalato)metallate trans-K3[RhCl2(C2O4)2]· 4 H2O und cis -K3[IrCl2(C2O4)2]· H2O

2000 ◽  
Vol 55 (6) ◽  
pp. 473-478
Author(s):  
J.-U. Rohde ◽  
W. Preetz
Keyword(s):  
Hydrogen Bonds ◽  
Electrostatic Interactions ◽  
Water Molecules ◽  
Monoclinic Space Group ◽  
Potassium Ions ◽  
Space Group ◽  
X Ray ◽  
Structure Determinations ◽  
Group 2 ◽  
Complex Anions

By treatment of RhCl3 or IrCl3 with K2C2O4 the bis(oxalato)metallates trans-K3[RhCl2(C2O4)2] and cis-K3[IrCl2(C2O4)2] are formed. From the aqueous solutions single crystals were grown by slow diffusion of ethanol and X-ray structure determinations of trans-K3[RhCl2(C2O4)2] · 4 H2O (monoclinic, space group I2/m, a = 6.218(1), b = 11.837(2), c - 10.357(2) Å, β = 95.55(3)°, Z = 2) and cis-K3[IrCl2(C2O4)2] · H2O (monoclinic, space group /2/a, a = 14.060(3), b = 7.586(2), c = 23.488(5) Å, β = 90.44(3)°, Z = 8) have been performed. The oxalato and chloro ligands of the complex anions are connected via hydrogen bonds and electrostatic interactions to water molecules and potassium ions. The potassium ions are eightfold and in one case ninefold coordinated.

Ethylenediammonium tetraaquabis(sulfato)cobaltate(II)

2007 ◽  
Vol 63 (11) ◽  
pp. m2643-m2644
Author(s):  
Patricia Leyva-Bailen ◽  
Anthony V. Powell ◽  
Paz Vaqueiro
Keyword(s):  
Hydrogen Bonds ◽  
Title Compound ◽  
Electrostatic Interactions ◽  
Three Dimensional ◽  
Octahedral Geometry ◽  
Water Molecules ◽  
Constituent Species ◽  
Dimensional Network

In the title compound, [NH3(CH2)2NH3][Co(SO4)2(H2O)4], both the cation and anion are centrosymmetric. The CoII ion adopts a slightly distorted CoO6 octahedral geometry, arising from four water molecules and two monodentate SO4 2− anions. In addition to electrostatic interactions, the constituent species are linked through N—H...O and O—H...O hydrogen bonds, forming a three-dimensional network.

scholarly journals Crystal structure of bis(acetato-κO)diaqua(2,2′-bipyridine-κ2N,N′)manganese(II)

2014 ◽  
Vol 70 (9) ◽  
pp. m326-m327 ◽  
Author(s):  
Natarajan Saravanan ◽  
Parasuraman Selvam
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Metal Ion ◽  
Water Molecules ◽  
Intramolecular Hydrogen Bonds ◽  
Distorted Octahedral Environment ◽  
Octahedral Environment ◽  
Π Stacking ◽  
Distorted Octahedral ◽  
Intramolecular Hydrogen

In the title monomeric manganese(II) complex, [Mn(CH3COO)2(C10H8N2)(H2O)2], the metal ion is coordinated by a bidentate 2,2′-bipyridine (bpy) ligand, two water molecules and two axial acetate anions, resulting in a highly distorted octahedral environment. The aqua ligands are stabilized by the formation of strong intramolecular hydrogen bonds with the uncoordinated acetate O atoms, giving rise to pseudo-bridging arrangement of the terminal acetate groups. In the crystal, the molecules form [010] zigzag chainsviaO—H...O hydrogen bonds involving the aqua ligands and acetate O atoms. Further, the water and bpy ligands aretransto each other, and are arranged in an off-set fashion showing intermolecular π–π stacking between nearly parallel bipy rings, the centroid–centroid separations being 3.8147 (12) and 3.9305 (13) Å.

scholarly journals Tetraaquabis(2,3-dihydro-1,4-benzodioxine-2-carboxylato)calcium(II)

IUCrData ◽  
2020 ◽  
Vol 5 (8) ◽  
Author(s):  
Esmit B. Camargo-Cortés ◽  
Mirna Acosta ◽  
Juan C. Martínez ◽  
Leslie W. Pineda
Keyword(s):  
Calcium Carbonate ◽  
Carboxylic Acid ◽  
Hydrogen Bonds ◽  
Title Compound ◽  
Metal Ion ◽  
Three Dimensional ◽  
Water Molecules ◽  
Acid Base ◽  
Carboxylate Ligands ◽  
Dimensional Network

The acid–base reaction of 1,4-benzodioxane 2-carboxylic acid with calcium carbonate furnished the centrosymmetric title compound, [Ca(C9H7O4)2(H2O)4], in which the metal ion is octahedrally coordinated by two monodentate 1,4-benzodioxane 2-carboxylate ligands and four water molecules. In the crystal, O—H...O and C—H...O hydrogen bonds link the molecules into a three-dimensional network.

scholarly journals THE COORDINATION COMPOUNDS Gd (III) AND Dy(III) WITH SOME β-DIKETONES

2021 ◽  
Vol 87 (6) ◽  
pp. 97-120
Author(s):  
Оeksandra Berezhnytska ◽  
Oleksandr Rohovtsov ◽  
Artur Horbenko ◽  
Yaroslav Fedorov ◽  
Olena Trunova ◽  
...  
Keyword(s):  
Electric Dipole Transition ◽  
Dipole Transition ◽  
Luminescence Spectra ◽  
Water Molecules ◽  
Emission Characteristics ◽  
Triplet Level ◽  
Resonant Level ◽  
Coordination Environment ◽  
Composition And Structure ◽  
Low Emission

New complexes of Dy (III) and Gd (III) with b-diketones containing unsaturated and aryl substituents were synthesized. Metal polymers based on synthesized complexes were obtained by the method of radical polymerization. The composition and structure of synthesized complexes and metal polymers are established. It is shown that during polymerization the coordination environment of the central ion remains unchanged. The spectral-luminescent cha­racteristics of the synthesized compounds were studied. The presence of water molecules in the immediate coordination environment causes a low intensity of emission of monomeric dysprosium complexes. In the luminescence spectra of metal polymers, there are bands magnetic dipole transition (4F9 → 6H15/2) and electric dipole transition (4F9 → 6H13/2). The close energies of the triplet level of the ligand and the resonant level of the dysprosium ion cause low emission characteristics of the synthesized dysprosium complexes.

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