Do halogen bonds dictate the packing preferences in solid solutions?

2017 ◽  
Vol 203 ◽  
pp. 201-212 ◽  
Author(s):  
Titas Pramanik ◽  
Mysore S. Pavan ◽  
Tayur N. Guru Row
Keyword(s):  
Solid Solution ◽  
Charge Density ◽  
Solid Solutions ◽  
Halogen Bond ◽  
Supramolecular Assembly ◽  
Differential Scanning Calorimetric ◽  
Type I ◽  
Halogen Bonds ◽  
Chlorobenzoic Acid ◽  
Stoichiometric Ratios

The isomeric compounds, 4-bromo-2-chloro benzoic acid (4Br) and 2-bromo-4-chlorobenzoic acid (2Br), crystallize in entirely different space groups, P21/n and P1̄ respectively. Both structures are stabilized by a strong O–H⋯O hydrogen bonds generating a carboxylic acid dimer along with an unusual triangular halogen bonded motif in the former and a well-defined halogen bond in the latter. Charge density analysis establishes the nature of halogen bonds by bringing out significant changes in the packing features of the two structures as well as the quantification of the interaction energies involved in the formation of the motifs. Cocrystallization efforts lead to the formation of solid solutions of varied stoichiometric ratios among the two entirely different crystalline forms, a feature which is observed for the first time, and depends on the nature of the halogen bonds. Despite the significant variations in the charge density distribution in intermolecular space, the triangular motif, with two type II Br⋯Cl and Cl⋯Br and one type I Br⋯Br contact in the structure of 4Br dictates the packing preferences in the solid solution as established by accurate single crystal diffraction studies supported by cognate powder diffraction analysis (PXRD) and differential scanning calorimetric (DSC) studies. A systematic study of the solid solution by varying the stoichiometric ratios establishes the hierarchy in halogen bonded motifs and consequently its directional influence to form the resultant supramolecular assembly.

Crystal packing and theoretical analysis of halogen- and hydrogen-bonded hydrazones from pharmaceuticals. Evidence of type I and II halogen bonds in extended chains of dichloromethane

2018 ◽  
Vol 74 (6) ◽  
pp. 618-627 ◽  
Author(s):  
Gilles Berger ◽  
Jalal Soubhye ◽  
René Wintjens ◽  
Koen Robeyns ◽  
Franck Meyer
Keyword(s):  
Crystal Packing ◽  
Interaction Strength ◽  
Supramolecular Assembly ◽  
Coupled Cluster ◽  
Type I ◽  
Energy Decomposition ◽  
Halogen Bonds ◽  
Linear Arrangement ◽  
X Ray ◽  
X Ray Crystallography

The supramolecular assembly of halogenated and hydroxyl hydrazones derived from two well known pharmaceuticals, isoniazid (IsX, where X = I, Br, OH) and hydralazine (HyX, where X = I, Br, OH), was studied by X-ray crystallography and theoretical methods. Crystal packing of IsI and HyI shows weak I...N and I...π halogen bonds, whereas the hydrogen bonds are dominant in the brominated scaffolds IsBr and HyBr. Although the calculated I...N interaction strength appears almost three times weaker than the O—H...N contacts in the isoniazid-based hydrazones, the higher directionality of the halogen bonds induces a linear and planar architecture of self-complementary tectons, observed only with the help of a bridging water molecule in the case of IsOH. Finally, the X-ray structure of HyOH is characterized by an unexpected linear arrangement of clathrated dichloromethane molecules bound through type I and II halogen bonds. This rare phenomenon, observed in less than ten structures, was studied by coupled cluster-based energy decomposition.

A comparative experimental and theoretical investigation of hydrogen-bond, halogen-bond and π–π interactions in the solid-state supramolecular assembly of 2- and 4-formylphenyl arylsulfonates

2018 ◽  
Vol 74 (7) ◽  
pp. 816-829 ◽  
Author(s):  
Hina Andleeb ◽  
Imtiaz Khan ◽  
Antonio Bauzá ◽  
Muhammad Nawaz Tahir ◽  
Jim Simpson ◽  
...  
Keyword(s):  
Solid State ◽  
Density Functional ◽  
Halogen Bond ◽  
Noncovalent Interactions ◽  
Supramolecular Assembly ◽  
Halogen Bonding ◽  
Type I ◽  
Supramolecular Architectures ◽  
Solid State Structures

To explore the operational role of noncovalent interactions in supramolecular architectures with designed topologies, a series of solid-state structures of 2- and 4-formylphenyl 4-substituted benzenesulfonates was investigated. The compounds are 2-formylphenyl 4-methylbenzenesulfonate, C14H12O4S, 3a, 2-formylphenyl 4-chlorobenzenesulfonate, C13H9ClO4S, 3b, 2-formylphenyl 4-bromobenzenesulfonate, C13H9BrO4S, 3c, 4-formylphenyl 4-methylbenzenesulfonate, C14H12O4S, 4a, 4-formylphenyl 4-chlorobenzenesulfonate, 4b, C13H9ClO4S, and 4-formylphenyl 4-bromobenzenesulfonate, C13H9BrO4S, 4c. The title compounds were synthesized under basic conditions from salicylaldehyde/4-hydroxybenzaldehydes and various aryl sulfonyl chlorides. Remarkably, halogen-bonding interactions are found to be important to rationalize the solid-state crystal structures. In particular, the formation of O...X (X = Cl and Br) and type I X...X halogen-bonding interactions have been analyzed by means of density functional theory (DFT) calculations and characterized using Bader's theory of `atoms in molecules' and molecular electrostatic potential (MEP) surfaces, confirming the relevance and stabilizing nature of these interactions. They have been compared to antiparallel π-stacking interactions that are formed between the arylsulfonates.

Crystalline assemblies of porphyrins with mixed bromophenyl and pyridyl meso-substituents and manifestation of supramolecular chirality induced by inter-porphyrin Br⋯N halogen bonds

2011 ◽  
Vol 15 (11n12) ◽  
pp. 1250-1257 ◽  
Author(s):  
Hatem M. Titi ◽  
Anirban Karmakar ◽  
Israel Goldberg
Keyword(s):  
Self Assembly ◽  
Halogen Bond ◽  
Supramolecular Assembly ◽  
Halogen Bonding ◽  
Building Blocks ◽  
Zinc Ion ◽  
Halogen Bonds ◽  
X Ray Diffraction ◽  
Supramolecular Chirality ◽  
Porphyrin Core

Four new crystalline solids based on the zinc-5,15-bis(4′-bromophenyl)-10,20- bis(4′-pyridyl)porphyrin ( Zn –DBDPyP) and zinc/copper-5,10,15-tris(4′-bromophenyl)-20-(4′-pyridyl)-porphyrin ( Zn/Cu –TBMPyP) platforms as building blocks, have been prepared and structurally analyzed by X-ray diffraction in order to examine whether the Br⋯N halogen bond can be effective in directing the supramolecular assembly of this functionalized porphyrins, in a similar way observed earlier for their iodophenyl-substituted analogs. The zinc ion in the porphyrin core was protected by an external ligand (pyridyl or methanol) to prevent its possible coordination to the pyridyl-porphyrin substituents. Neither the bis-pyridyl Zn (py)–DBDPyP scaffold nor the Zn(MeOH)/Cu –TBMPyP exhibited inter-porphyrin halogen bonding in their corresponding crystals. Only the layered self-assembly of the Zn (py)–TBMPyP building block was found to be uniquely directed by Br⋯N halogen bonds, as well as by Br⋯Br and Br⋯π interactions. This observation supports our notion that asymmetric functionalization of the tetraarylporphyrin scaffold, combined with directional interporphyrin interactions (as halogen bonding), represent a promising approach to supramolecular chirality.

scholarly journals Synthesis of Ce1−xPdxO2−δ Solid Solution in Molten Nitrate

Catalysts ◽  
2020 ◽  
Vol 10 (6) ◽  
pp. 640
Author(s):  
Hideaki Sasaki ◽  
Keisuke Sakamoto ◽  
Masami Mori ◽  
Tatsuaki Sakamoto
Keyword(s):  
Electron Microscopy ◽  
Solid Solution ◽  
Solid Solutions ◽  
Photoelectron Spectroscopy ◽  
Synthesis Method ◽  
X Ray Diffraction ◽  
X Ray ◽  
Transmission Electron ◽  
Co Precipitation ◽  
Ionic States

CeO2-based solid solutions in which Pd partially substitutes for Ce attract considerable attention, owing to their high catalytic performances. In this study, the solid solution (Ce1−xPdxO2−δ) with a high Pd content (x ~ 0.2) was synthesized through co-precipitation under oxidative conditions using molten nitrate, and its structure and thermal decomposition were examined. The characteristics of the solid solution, such as the change in a lattice constant, inhibition of sintering, and ionic states, were examined using X-ray diffraction (XRD), scanning electron microscopy–energy-dispersive X-ray spectroscopy (SEM−EDS), transmission electron microscopy (TEM)−EDS, and X-ray photoelectron spectroscopy (XPS). The synthesis method proposed in this study appears suitable for the easy preparation of CeO2 solid solutions with a high Pd content.

Electron microprobe study of turquoise-group solid solutions in the Neyshabour and Meydook mines, northeast and southern Iran

2020 ◽  
Vol 58 (1) ◽  
pp. 71-83
Author(s):  
Elahe Mansouri Gandomani ◽  
Nematollah Rashidnejad-Omran ◽  
Amir Emamjomeh ◽  
Pietro Vignola ◽  
Tahereh Hashemzadeh
Keyword(s):  
Solid Solution ◽  
Solid Solutions ◽  
Electron Microprobe ◽  
Electron Probe Microanalysis ◽  
Electron Probe ◽  
Major Elements ◽  
Point Of View ◽  
Chemical Compositions ◽  
Light Blue ◽  
Quaternary Solid Solution

ABSTRACT Turquoise, CuAl6(PO4)4(OH)8·4H2O, belongs to the turquoise group, which consists of turquoise, chalcosiderite, aheylite, faustite, planerite, and UM1981-32-PO:FeH. In order to study turquoise-group solid solutions in samples from the Neyshabour and Meydook mines, 17 samples were selected and investigated using electron probe microanalysis. In addition, their major elements were compared in order to evaluate the feasibility of distinguishing the provenance of Persian turquoises. The electron microprobe data show that the studied samples are not constituted of pure turquoise (or any other pure endmember) and belong, from the chemical point of view, to turquoise-group solid solutions. In a turquoise–planerite–chalcosiderite–unknown mineral quaternary solid solution diagram, the chemical compositions of the analyzed samples lie along the turquoise–planerite line with minor involvement of chalcosiderite and the unknown mineral. Among light blue samples with varying hues and saturations from both studied areas, planerite is more abundant among samples from Meydook compared with samples from Neyshabour. Nevertheless, not all the light blue samples are planerite. This study demonstrates that distinguishing the deposit of origin for isochromatic blue and green turquoises, based on electron probe microanalysis method and constitutive major elements, is not possible.

Epitaxial Solid-Solution Films of Immiscible MgO and CaO

1994 ◽  
Vol 341 ◽  
Author(s):  
E. S. Hellman ◽  
E. H. Hartford
Keyword(s):  
Solid Solution ◽  
Molecular Beam Epitaxy ◽  
Lattice Constant ◽  
Solid Solutions ◽  
Molecular Beam ◽  
Building Blocks ◽  
Layer Growth ◽  
Growth Mode ◽  
Miscibility Gap ◽  
Layer By Layer

AbstractMetastable solid-solutions in the MgO-CaO system grow readily on MgO at 300°C by molecular beam epitaxy. We observe RHEED oscillations indicating a layer-by-layer growth mode; in-plane orientation can be described by the Matthews theory of island rotations. Although some films start to unmix at 500°C, others have been observed to be stable up to 900°C. The Mgl-xCaxO solid solutions grow despite a larger miscibility gap in this system than in any system for which epitaxial solid solutions have been grown. We describe attempts to use these materials as adjustable-lattice constant epitaxial building blocks

Intermolecular binding preferences of haloethynyl halogen-bond donors as a function of molecular electrostatic potentials in a family of N-(pyridin-2-yl)amides

2021 ◽  
Author(s):  
Amila M. Abeysekera ◽  
Boris B. Averkiev ◽  
Pierre Le Magueres ◽  
Christer B. Aakeröy
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Halogen Bond ◽  
Electrostatic Potentials ◽  
Halogen Bonds ◽  
Molecular Electrostatic Potentials

The roles played by halogen bonds and hydrogen bonds in the crystal structures of N-(pyridin-2-yl)amides were evaluated and rationalised in the context of calculated molecular electrostatic potentials.

Cationic Substitutions in Sphalerite from the Porgera Mine, Papua New Guinea

2021 ◽  
Author(s):  
Christopher H. Ingles ◽  
John A. Mavrogenes
Keyword(s):  
Solid Solution ◽  
Papua New Guinea ◽  
Solid Solutions ◽  
Inductively Coupled Plasma ◽  
New Guinea ◽  
Inductively Coupled ◽  
Cationic Substitution ◽  
Plasma Mass Spectrometry ◽  
Positive Correlations

ABSTRACT Laser ablation-inductively coupled plasma-mass spectrometry was used to traverse hydrothermal vein sphalerite from different ore-forming stages of the Porgera Au-Ag mine, Papua New Guinea. Elements were measured in situ over the growth of crystals to investigate the greatly varying concentrations of cations in sphalerite and their positions in the lattice. Traverse profiles for 16 elements were obtained and aligned to transmitted light images where possible. Each sample contained an array of elements, with many displaying orders of magnitude concentration differences. Results show the simultaneous incorporation of Cu and Sn in sphalerite, as well as Cu and Ag, In and Sn, As and Sb, Fe and Mn, and Cu and Ga. The relation [4Zn2+ ↔ 2Cu+ + Sn2+ + Sn4+] is proposed to explain the 1:1 Cu–Sn correlation. Further relations can be seen, including a Ga “ceiling” or Cu “floor”, where Ga incorporation becomes dependent on Cu concentrations. Furthermore, silver was also observed to correlate with Au, Mn, Ni, Pb, and Bi. Meta-stable solid solutions between pairs such as Cu, Ag; Fe, Mn; As, Sb; and In, Sn are also suggested. Each of these pairs are neighbors on the periodic table of elements, which suggests that simple solid solution can occur, and positive correlations for all four solid solutions were found in one sample alone. While the concept of charge-specific solid solutions in sphalerite has been discussed in the literature with reference to monovalent cations, the results presented herein also indicate solid solutions of higher oxidation states, containing many cations. Furthermore, while cations in charge-specific solid solutions have been proposed to compete for lattice sites in sphalerite, simultaneous in situ coupled concentrations at Porgera suggest otherwise. Cationic substitution equations displaying decimal ratios of each element in solid solution can then provide a novel method to distinguish between solid solution concentrations in different samples. For example, displaying 1:1 ratios of Cu–Ag and Sb–As: [2Zn2+ ↔ (Cu+0.5, Ag+0.5) + (As3+0.5, Sb3+0.5)], or for a 100:1 Fe–Mn ratio: [Zn2+ ↔ (Fe2+0.99, Mn2+0.01)].

Neutron Diffraction Studies on the Structure and Conduction Mechanism in Al, Ga—DOPED Li4SiO4

1990 ◽  
Vol 210 ◽  
Author(s):  
R.I. Smith ◽  
A.R. West
Keyword(s):  
Solid Solution ◽  
Neutron Diffraction ◽  
Solid Solutions ◽  
Conduction Mechanism ◽  
One Dimensional ◽  
Linear Defects ◽  
Solution Mechanism

AbstractCrystallographic results on the Li4-3x(Al,Ga)xSiO4 solid solutions are reviewed. The six sets of sites available for Li+ ions fall into two groups. The ‘framework’ sites, which also contain the substitutional Al,Ga ions, appear to have little effect on conductivity. The ‘channel’sites contain varying amounts of Li+ ions and are responsible for the dramatic variations in conductivity with x. There is evidence for the presence of one—dimensional defects, comprising columns of ordered Li+ ions, in both the framework and channel sites. The relative numbers of these linear defects has a large bearing on the solid solution mechanism in the framework sites and their occurrence in the channel sites may be responsible for the low conductivity in stoichiometric Li4SiO4.

Synthesis of ZrO2–Y6WO12 solid solution powders by a polymerized complex method

1998 ◽  
Vol 13 (4) ◽  
pp. 939-943 ◽  
Author(s):  
Junfeng Ma ◽  
Masahiro Yoshimura ◽  
Masato Kakihana ◽  
Masatomo Yashima
Keyword(s):  
Solid Solution ◽  
Crystallite Size ◽  
Surface Area ◽  
Solid Solutions ◽  
Lattice Parameter ◽  
Cubic Phase ◽  
Complex Method ◽  
Amorphous Precursor ◽  
Fine Powders ◽  
Polymerized Complex Method

A series of solid solutions (1 − x) ZrO2 · xY0.857 W0.143 O1.714 (1/7Y6WO12) of metastable cubic phase were synthesized at 800 °C through a polymerized complex method. Lattice parameter a0 of solid solutions varies linearly with Y0.857 W0.143 O1.714 content (x). Crystallization began to occur above 400 °C from amorphous precursor to yield at 800 °C fine powders of 6–10 nm and 19–40 m2/g for crystallite size and surface area, respectively.

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