scholarly journals Building inorganic supramolecular architectures using principles adopted from the organic solid state

IUCrJ ◽  
2018 ◽  
Vol 5 (1) ◽  
pp. 13-21 ◽  
Author(s):  
Marijana Đaković ◽  
Željka Soldin ◽  
Boris-Marko Kukovec ◽  
Ivan Kodrin ◽  
Christer B. Aakeröy ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Molecular Electrostatic Potential ◽  
Building Blocks ◽  
Coordination Complexes ◽  
Potential Surfaces ◽  
Supramolecular Architectures ◽  
Organic Solid ◽  
Complex Building

In order to develop transferable and practical avenues for the assembly of coordination complexes into architectures with specific dimensionality, a strategy utilizing ligands capable of simultaneous metal coordination and self-complementary hydrogen bonding is presented. The three ligands used, 2(1H)-pyrazinone, 4(3H)-pyrimidinone and 4(3H)-quinazolinone, consistently deliver the required synthetic vectors in a series of CdII coordination polymers, allowing for reproducible supramolecular synthesis that is insensitive to the different steric and geometric demands from potentially disruptive counterions. In all nine crystallographically characterized compounds presented here, directional intermolecular N—H...O hydrogen bonds between ligands on adjacent complex building blocks drive the assembly and orientation of discrete building blocks into largely predictable topologies. Furthermore, whether the solids are prepared from solution or through liquid-assisted grinding, the structural outcome is the same, thus emphasizing the robustness of the synthetic protocol. The details of the molecular recognition events that take place in this series of compounds have been clearly delineated and rationalized in the context of calculated molecular electrostatic potential surfaces.

Conformational control through co-operative nonconventional C—H...N hydrogen bonds

2021 ◽  
Vol 77 (8) ◽  
Author(s):  
Eric Bosch ◽  
Nathan P. Bowling ◽  
Shalisa M. Oburn
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Surface Analysis ◽  
Electrostatic Potential ◽  
Molecular Electrostatic Potential ◽  
Hirshfeld Surface ◽  
Design Synthesis ◽  
Synthesis And Crystal Structure

We report the design, synthesis, and crystal structure of a conjugated aryleneethynyl molecule, 2-(2-{4,5-dimethoxy-2-[2-(2,3,4-trifluorophenyl)ethynyl]phenyl}ethynyl)-6-[2-(pyridin-2-yl)ethynyl]pyridine, C30H17F3N2O2, that adopts a planar rhombus conformation in the solid state. The molecule crystallizes in the space group P\overline{1}, with Z = 2, and features two intramolecular sp2 -C—H...N hydrogen bonds that co-operatively hold the arylethynyl molecule in a rhombus conformation. The H atoms are activated towards hydrogen bonding since they are situated on a trifluorophenyl ring and the H...N distances are 2.470 (16) and 2.646 (16) Å, with C—H...N angles of 161.7 (2) and 164.7 (2)°, respectively. Molecular electrostatic potential calculations support the formation of C—H...N hydrogen bonds to the trifluorophenyl moiety. Hirshfeld surface analysis identifies a self-complementary C—H...O dimeric interaction between adjacent 1,2-dimethoxybenzene segments that is shown to be common in structures containing that moiety.

Heteropolymetallic Supramolecular Solid-State Architectures Constructed from Dicyanoaurate Ion, Phen, and 3d Metals

2006 ◽  
Vol 59 (9) ◽  
pp. 640 ◽  
Author(s):  
Gong-Feng Xu ◽  
Zhan-Quan Liu ◽  
Hui-Bo Zhou ◽  
Yang Guo ◽  
Dai-Zheng Liao
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Self Assembly ◽  
Three Dimensional ◽  
Coordination Complexes ◽  
Assembly Process ◽  
Π Interactions ◽  
3D Metals ◽  
Supramolecular Architectures ◽  
Polymeric Coordination

Two new supramolecular polymeric coordination complexes, {Zn(phen)2[Au2(CN)4](H2O)}·1.5H2O 1 and {Mn(phen)[Au2(CN)4](H2O)}·PriOH 2, have been obtained through a self-assembly process. The three-dimensional supramolecular architectures of compounds 1 and 2 are sustained by aurophilic, hydrogen-bonding, and/or π–π interactions. Gold atoms linked with aurophilic bonds arrange in a pattern not frequently observed.

Synthesis and supramolecular organization of the iodide and triiodides of a polycyclic adamantane-based diammonium cation: the effects of hydrogen bonds and weak I⋯I interactions

CrystEngComm ◽  
2021 ◽  
Vol 23 (12) ◽  
pp. 2384-2395
Author(s):  
Ivan A. Mezentsev-Cherkes ◽  
Tatiana A. Shestimerova ◽  
Aleksei V. Medved'ko ◽  
Mikhail A. Kalinin ◽  
Alexey N. Kuznetsov ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Building Blocks ◽  
Supramolecular Organization ◽  
Supramolecular Architectures

Adamantane-like divalent building blocks and iodide or polyiodide anions combine into supramolecular architectures with the help of various noncovalent forces ranging from strong hydrogen bonds to secondary and weak I⋯I interactions.

scholarly journals Temperature-Dependent Solid-State NMR Proton Chemical-Shift Values and Hydrogen Bonding

2021 ◽  
Author(s):  
Alexander A. Malär ◽  
Laura A. Völker ◽  
Riccardo Cadalbert ◽  
Lauriane Lecoq ◽  
Matthias Ernst ◽  
...  
Keyword(s):  
Magnetic Field ◽  
Hydrogen Bonding ◽  
Solid State ◽  
Chemical Shift ◽  
Hydrogen Bonds ◽  
Solid State Nmr ◽  
Magic Angle Spinning ◽  
Magic Angle ◽  
Proton Chemical Shift ◽  
Temperature Dependent

Temperature-dependent NMR experiments are often complicated by rather long magnetic-field equilibration times, for example occurring upon a change of sample temperature. We demonstrate that the fast temporal stabilization of the magnetic field can be achieved by actively stabilizing the temperature which allows to quantify the weak temperature dependence of the proton chemical shift which can be diagnostic for the presence of hydrogen bonds. Hydrogen bonding plays a central role in molecular recognition events from both fields, chemistry and biology. Their direct detection by standard structure determination techniques, such as X-ray crystallography or cryo-electron microscopy, remains challenging due to the difficulties of approaching the required resolution, on the order of 1 Å. We herein explore a spectroscopic approach using solid-state NMR to identify protons engaged in hydrogen bonds and explore the measurement of proton chemical-shift temperature coefficients. Using the examples of a phosphorylated amino acid and the protein ubiquitin, we show that fast Magic-Angle Spinning (MAS) experiments at 100 kHz yield sufficient resolution in proton-detected spectra to quantify the rather small chemical-shift changes upon temperature variations.<br>

Supramolecular architectures in two 1:1 cocrystals of 5-fluorouracil with 5-bromothiophene-2-carboxylic acid and thiophene-2-carboxylic acid

2017 ◽  
Vol 73 (6) ◽  
pp. 481-485 ◽  
Author(s):  
Marimuthu Mohana ◽  
Packianathan Thomas Muthiah ◽  
Colin D. McMillen
Keyword(s):  
Solid State ◽  
Carboxylic Acid ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
X Ray Diffraction ◽  
Base Pairs ◽  
X Ray ◽  
Supramolecular Architectures ◽  
Acid Acid ◽  
Carboxylic Acid Dimer

In solid-state engineering, cocrystallization is a strategy actively pursued for pharmaceuticals. Two 1:1 cocrystals of 5-fluorouracil (5FU; systematic name: 5-fluoro-1,3-dihydropyrimidine-2,4-dione), namely 5-fluorouracil–5-bromothiophene-2-carboxylic acid (1/1), C5H3BrO2S·C4H3FN2O2, (I), and 5-fluorouracil–thiophene-2-carboxylic acid (1/1), C4H3FN2O2·C5H4O2S, (II), have been synthesized and characterized by single-crystal X-ray diffraction studies. In both cocrystals, carboxylic acid molecules are linked through an acid–acid R 2 2(8) homosynthon (O—H...O) to form a carboxylic acid dimer and 5FU molecules are connected through two types of base pairs [homosynthon, R 2 2(8) motif] via a pair of N—H...O hydrogen bonds. The crystal structures are further stabilized by C—H...O interactions in (II) and C—Br...O interactions in (I). In both crystal structures, π–π stacking and C—F...π interactions are also observed.

The influence of hydrogen bonding on the character of N—H and C=O stretching modes in 2-thiopyrrole-1,2-dicarboximide

1984 ◽  
Vol 62 (9) ◽  
pp. 1845-1849 ◽  
Author(s):  
Shanker Ram
Keyword(s):  
Hydrogen Bonding ◽  
Transition Temperature ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Spectral Data ◽  
Infrared Spectra ◽  
Cyclic Dimer ◽  
Dilute Solutions ◽  
Two Phases ◽  
Thermodynamical Functions

The infrared spectra (200–4000 cm−1) of 2-thiopyrrole-1,2-dicarboximide (TPH) in solid and solution forms have been measured as a function of temperature, and a direct correlation has been obtained between the two phases and the type and extent of hydrogen bonding. It is suggested that TPH exists as cyclic dimer in the solid state (below 310 K) and in dilute solutions by the formation of two equivalent hydrogen bonds. At the transition temperature, ~310 K, the cyclic dimer undergoes to the open-cyclic dimer and persists in this structure till 410 K. In addition, the thermodynamical functions ΔH0, and ΔS0 have been estimated using the spectral data in solution.

The design of artificial receptors for complexation and controlled aggregation

1993 ◽  
Vol 345 (1674) ◽  
pp. 57-66 ◽  
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Complex Formation ◽  
Hydrogen Bonds ◽  
Synthetic Receptors ◽  
Polar Solvents ◽  
Artificial Receptors ◽  
Hydrogen Bonding Interactions ◽  
Number Of Factors ◽  
Network Of Hydrogen Bonds

Simple synthetic receptors have been developed that function via directed hydrogen bonding interactions in highly competitive solvents. Strong binding of this type in polar solvents may be due to a number of factors including favourable secondary hydrogen bonding interactions between the carboxylate and urea, the use of charged H-bond acceptors, an inefficient solvation of the closely spaced H-bond donor sites in the urea, and an entropically favourable release of solvent and/or counterion molecules on complex formation. We also demonstrate that these types of interactions can be used to induce, both in solution and the solid state, discrete 2 + 2 aggregates stabilized by a network of hydrogen bonds.

scholarly journals Exploration and exploitation of homologous series of bis(acrylamido)alkanes containing pyridyl and phenyl groups: β-sheetversustwo-dimensional layers in solid-state photochemical [2 + 2] reactions

IUCrJ ◽  
2015 ◽  
Vol 2 (5) ◽  
pp. 523-533 ◽  
Author(s):  
Mousumi Garai ◽  
Kumar Biradha
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Single Crystal ◽  
Crystal Structures ◽  
Homologous Series ◽  
Bonding Layer ◽  
Two Dimensional ◽  
Systematic Analysis ◽  
Small Change

The homologous series of phenyl and pyridyl substituted bis(acrylamido)alkanes have been synthesized with the aim of systematic analysis of their crystal structures and their solid-state [2 + 2] reactivities. The changes in the crystal structures with respect to a small change in the molecular structure, that is by varying alkyl spacers between acrylamides and/or by varying the end groups (phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl) on the C-terminal of the amide, were analyzed in terms of hydrogen-bonding interference (N—H...NpyversusN—H...O=C) and network geometries. In this series, a greater tendency towards the formation of N—H...O hydrogen bonds (β-sheets and two-dimensional networks) over N—H...N hydrogen bonds was observed. Among all the structures seven structures were found to have the required alignments of double bonds for the [2 + 2] reaction such that the formations of single dimer, double dimer and polymer are facilitated. However, only four structures were found to exhibit such a solid-state [2 + 2] reaction to form a single dimer and polymers. The two-dimensional hydrogen-bonding layerviaN—H...O hydrogen bonds was found to promote solid-state [2 + 2] photo-polymerization in a single-crystal-to-single-crystal manner. Such two-dimensional layers were encountered only when the spacer between acryl amide moieties is butyl. Only four out of the 16 derivatives were found to form hydrates, two each from 2-pyridyl and 4-pyridyl derivatives. The water molecules in these structures govern the hydrogen-bonding networks by the formation of an octameric water cluster and one-dimensional zigzag water chains. The trends in the melting points and densities were also analyzed.

Structure and hydrogen bonding in 2,4-dihydroxybenzoic acid at 90, 100, 110 and 150 K; a theoretical and single-crystal X-ray diffraction study

2007 ◽  
Vol 63 (2) ◽  
pp. 303-308 ◽  
Author(s):  
Andrew Parkin ◽  
Martin Adam ◽  
Richard I. Cooper ◽  
Derek S. Middlemiss ◽  
Chick C. Wilson
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Hydrogen Bonds ◽  
X Ray Diffraction ◽  
Dihydroxybenzoic Acid ◽  
X Ray ◽  
Hydrogen Bond System ◽  
Proton Disorder ◽  
Intramolecular Hydrogen ◽  
Carboxylic Acid Dimer

A new polymorph of 2,4-dihydroxybenzoic acid is reported. The structure was characterized by multiple-temperature X-ray diffraction and solid-state DFT computations. The material shows a geometric pattern of hydrogen bonding consistent with cooperativity between the intermolecular carboxylic acid dimer and intramolecular hydrogen bonds. The presence of proton disorder within this hydrogen-bond system, which would support such a cooperative model, was not fully ruled out by the initial X-ray studies. However, solid-state calculations on the three possible end-point tautomers indicate that the dominant crystallographically observed configuration is substantially lower in energy than the other tautomers (by at least 9 kJ mol−1), indicating that no disorder should be expected. It is therefore concluded that no disorder is observed either in the intra- or intermolecular hydrogen bonds of the title compound and that the cooperativity between the hydrogen bonds is not present within the temperature range studied.

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