scholarly journals 1,4-Dibromo-2,5-bis(phenylalkoxy)benzene Derivatives: C–Br...π(arene) Versus C–H...Br and Br...Br Interactions in the Solid State

Crystals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 325
Author(s):  
Giacomo Manfroni ◽  
Alessandro Prescimone ◽  
Edwin Constable ◽  
Catherine Housecroft
Keyword(s):  
Solid State ◽  
Hydrogen Bonds ◽  
Single Crystal ◽  
Crystal Structures ◽  
Molecular Level ◽  
Benzene Derivatives ◽  
Single Crystal Structures ◽  
Π Stacking ◽  
Adjacent Molecule ◽  
Packing Interactions

We have prepared and characterized 1,4-dibromo-2,5-bis(2-phenylethoxy)benzene (1) and 1,4-dibromo-2,5-bis(3-phenylpropoxy)benzene (2). Their single-crystal structures confirm that, at the molecular level, they are similar with the phenylalkoxy chains in extended conformations. However, there are significant differences in packing interactions. The packing in 1 is dominated by C–Br...π(arene) interactions, with each Br located over one C–C bond of the central arene ring of an adjacent molecule. In contrast, the packing of molecules of 2 involves a combination of C–H...Br hydrogen bonds, Br...Br interactions, and arene–arene π-stacking. The single-crystal structures of both orthorhombic and triclinic polymorphs of 1 have been determined and the packing interactions are shown to be essentially identical.

scholarly journals Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu2(μ-OAc)4(3,2′:6′,3″-tpy)]n 1D-Polymers

Chemistry ◽  
2021 ◽  
Vol 3 (1) ◽  
pp. 182-198
Author(s):  
Dalila Rocco ◽  
Samantha Novak ◽  
Alessandro Prescimone ◽  
Edwin C. Constable ◽  
Catherine E. Housecroft
Keyword(s):  
Single Crystal ◽  
Crystal Structures ◽  
Metal Binding ◽  
Polymer Chains ◽  
X Ray Diffraction ◽  
Face To Face ◽  
Single Crystal Structures ◽  
Π Stacking ◽  
Metal Binding Domain ◽  
Packing Interactions

We report the preparation and characterization of 4′-([1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (1), 4′-(4′-fluoro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (2), 4′-(4′-chloro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (3), 4′-(4′-bromo-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (4), and 4′-(4′-methyl-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (5), and their reactions with copper(II) acetate. Single-crystal structures of the [Cu2(μ-OAc)4L]n 1D-coordination polymers with L = 1–5 have been determined, and powder X-ray diffraction confirms that the single crystal structures are representative of the bulk samples. [Cu2(μ-OAc)4(1)]n and [Cu2(μ-OAc)4(2)]n are isostructural, and zigzag polymer chains are present which engage in π-stacking interactions between [1,1′-biphenyl]pyridine units. 1D-chains nest into one another to give 2D-sheets; replacing the peripheral H in 1 by an F substituent in 2 has no effect on the solid-state structure, indicating that bifurcated contacts (H...H for 1 or H...F for 2) are only secondary packing interactions. Upon going from [Cu2(μ-OAc)4(1)]n and [Cu2(μ-OAc)4(2)]n to [Cu2(μ-OAc)4(3)]n, [Cu2(μ-OAc)4(4)]n, and [Cu2(μ-OAc)4(5)]n·nMeOH, the increased steric demands of the Cl, Br, or Me substituent induces a switch in the conformation of the 3,2′:6′,3″-tpy metal-binding domain, and a concomitant change in dominant packing interactions to py–py and py–biphenyl face-to-face π-stacking. The study underlines how the 3,2′:6′,3″-tpy domain can adapt to different steric demands of substituents through its conformational flexibility.

scholarly journals Switching the Conformation of 3,2′:6′,3″-tpy Domains in 4′-(4-n-Alkyloxyphenyl)-3,2′:6′,3″-Terpyridines

Molecules ◽  
2020 ◽  
Vol 25 (14) ◽  
pp. 3162 ◽  
Author(s):  
Dalila Rocco ◽  
Alessandro Prescimone ◽  
Edwin C. Constable ◽  
Catherine E. Housecroft
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Crystal Structures ◽  
Dominant Role ◽  
Van Der Waals Interactions ◽  
Single Crystal Structures ◽  
Solid State Structures ◽  
Packing Interactions ◽  
Adjacent Sheet

The preparation and characterization of 4′-(4-n-octyloxyphenyl)-3,2′:6′,3″-terpyridine (8) and 4′-(4-n-nonyloxyphenyl)-3,2′:6′,3″-terpyridine (9) are reported. The single crystal structures of 4′-(4-n-hexyloxyphenyl)-3,2′:6′,3″-terpyridine (6), 4′-(4-n-heptyloxyphenyl)-3,2′:6′,3″-terpyridine (7), and compounds 8 and 9 have been determined. The conformation of the 3,2′:6′,3″-tpy unit is trans,trans in 6 and 7, but switches to cis,trans in 8 and 9. This is associated with significant changes in the packing interactions with a more dominant role for van der Waals interactions between adjacent n-alkyloxy chains and C–Hmethylene... π interactions in 8 and 9. The solid-state structures of 6 and 7 with the n-hexyloxy and n-heptyloxy chains feature interwoven sheets of supramolecular assemblies of molecules, with pairs of n-alkyloxy chains threaded through cavities in an adjacent sheet.

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.

Crystallisation-Driven Self-Sorting of H-Bonded Guanidinium or Sodium Sulfonate Constitutional Molecular Frameworks

2014 ◽  
Vol 67 (7) ◽  
pp. 1005 ◽  
Author(s):  
Dan Dumitrescu ◽  
Yves-Marie Legrand ◽  
Nathalie Masquelez ◽  
Arie van der Lee ◽  
Mihail Barboiu
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Crystal Structures ◽  
Sodium Salt ◽  
Crystalline State ◽  
Sodium Sulfonate ◽  
Single Crystal Structures ◽  
Sodium Cations ◽  
The Difference

Four single crystal structures were obtained in order to better understand the difference between the crystallisation-driven formation of solid state organo-sulfonate guanidinium superstructures and their sodium salt analogues. 5-Formyl-2-furfuryl sulfonate and 4,4′-diamino-2,2′-biphenyl disulfonate were chosen as anions due to functional and geometrical considerations together with guanidinium, aminoguanidinium, and sodium cations. 5-Formyl-2-fufuryl sulfonate reacts with aminoguanidinium cation in water leading to an imino-zwitterionic compound, able to form on its own a guanidinium-sulfonate superstructure in crystalline state.

scholarly journals Synthesis and X-Ray Single Crystal Structures of Cadmiym(II) Complexes: CdCl2[CS(NHCH3)2]2and CdCl2(CS(NH2)NHC6H5)4-Single Source Precursors to CdS Nanoparticles

2010 ◽  
Vol 7 (4) ◽  
pp. 1148-1155 ◽  
Author(s):  
M. J. Moloto ◽  
N. Revaprasadu ◽  
G. A. Kolawole ◽  
P. O’brien ◽  
M. A. Malik ◽  
...  
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Crystal Structures ◽  
Trioctylphosphine Oxide ◽  
Cds Nanoparticles ◽  
Single Source ◽  
Distorted Tetrahedron ◽  
X Ray ◽  
Single Crystal Structures ◽  
Single Source Precursor

Two new cadmium(II) complexes CdCl2[CS(NHCH3)2]2(1) and CdCl2(CS(NH2)NHC6H5)4(2) have been synthesized and characterized by spectroscopic and x-ray crystallographic methods. Both compounds are monomers in the solid state with the four and six coordinate and their coordination geometries based on distorted tetrahedron and distorted octahedron respectively. The thiourea ligands behave as monodentate in both compounds with the binding through sulfur. Complex (2) is one of the few examples of monomeric six coordinate Cd(II) complexes with four monodentate thiourea and two chloride ligands. The Cd-S bond proved useful as a source of preparing nanoparticles using these complexes as single source precursor at a temperature of 250 °C in trioctylphosphine oxide (TOPO).

4-Substituted 3,6-Bis(2-pyridyl)pyridazines: Silver(I) Complexes of 4-Cyano- and 4-(4-Bromophenyl)-3,6-bis(2-pyridyl)pyridazine and Pseudopolymorphs of 1,3,5-Tris{3,6-bis(2-pyridyl)pyridazin-4-yl}benzene

2008 ◽  
Vol 61 (11) ◽  
pp. 847 ◽  
Author(s):  
Edwin C. Constable ◽  
Catherine E. Housecroft ◽  
Markus Neuburger ◽  
Sébastien Reymann ◽  
Silvia Schaffner
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Crystal Structures ◽  
Model Structure ◽  
State Structure ◽  
Ligand Environment ◽  
Solid State Structure ◽  
Single Crystal Structures

Metal:ligand complexes are crystallized from reaction mixtures of equimolar amounts of 4-cyano-3,6-bis(2-pyridyl)pyridazine 2 or 4-(4-bromophenyl)-3,6-bis(2-pyridyl)pyridazine 3 and silver(i) triflate. In [Ag2(2)2]2+, the two ligands adopt a head-to-tail arrangement, while a head-to-head motif is confirmed for the solid state structure of [Ag2(3)2]2+. In solution, one ligand environment is observed in each case. Silver(i) reacts with 1,3,5-tris{3,6-bis(2-pyridyl)pyridazin-4-yl}benzene 4 to give highly insoluble powders. The single crystal structures of the pseudopolymorphs (4)·Et2O and 2(4)·2MeCN·H2O are reported; in each structure, the ligand adopts the same conformation, derived from a Cs rather than C3v model structure.

scholarly journals Isomeric 4,2′:6′,4″- and 3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl Substituents: Effects on the Assembly of Coordination Polymers with [Cu(hfacac)2] (Hhfacac = Hexafluoropentane-2,4-dione)

Inorganics ◽  
2021 ◽  
Vol 9 (7) ◽  
pp. 54
Author(s):  
Giacomo Manfroni ◽  
Simona S. Capomolla ◽  
Alessandro Prescimone ◽  
Edwin C. Constable ◽  
Catherine E. Housecroft
Keyword(s):  
Coordination Polymers ◽  
Metal Binding ◽  
Polymer Chains ◽  
Stacking Interactions ◽  
X Ray Diffraction ◽  
Preparative Scale ◽  
X Ray ◽  
Single Crystal Structures ◽  
Π Stacking ◽  
Packing Interactions

The isomers 4′-(4-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (1), 4′-(3-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (2), 4′-(4-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (3), and 4′-(3-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (4) have been prepared and characterized. The single crystal structures of 1 and 2 were determined. The 1D-polymers [Cu2(hfacac)4(1)2]n.2nC6H4Cl2 (Hhfacac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione), [Cu(hfacac)2(2)]n.2nC6H5Me, [Cu2(hfacac)4(3)2]n.nC6H4Cl2, [Cu2(hfacac)4(3)2]n.nC6H5Cl, and [Cu(hfacac)2(4)]n.nC6H5Cl have been formed by reactions of 1, 2, 3 and 4 with [Cu(hfacac)2].H2O under conditions of crystal growth by layering and four of these coordination polymers have been formed on a preparative scale. [Cu2(hfacac)4(1)2]n.2nC6H4Cl2 and [Cu(hfacac)2(2)]n.2nC6H5Me are zig-zag chains and the different substitution position of the CF3 group in 1 and 2 does not affect this motif. Packing of the polymer chains is governed mainly by C–F...F–C contacts, and there are no inter-polymer π-stacking interactions. The conformation of the 3,2′:6′,3″-tpy unit in [Cu2(hfacac)4(3)2]n.nC6H4Cl2 and [Cu(hfacac)2(4)]n.nC6H5Cl differs, leading to different structural motifs in the 1D-polymer backbones. In [Cu(hfacac)2(4)]n.nC6H5Cl, the peripheral 3-CF3C6H4 unit is accommodated in a pocket between two {Cu(hfacac)2} units and engages in four C–Hphenyl...F–Chfacac contacts which lock the phenylpyridine unit in a near planar conformation. In [Cu2(hfacac)4(3)2]n.nC6H4Cl2 and [Cu(hfacac)2(4)]n.nC6H5Cl, π-stacking interactions between 4′-trifluoromethylphenyl-3,2′:6′,3″-tpy domains are key packing interactions, and this contrasts with the packing of polymers incorporating 1 and 2. We use powder X-ray diffraction to demonstrate that the assemblies of the coordination polymers are reproducible, and that a switch from a 4,2′:6′,4″- to 3,2′:6′,3″-tpy metal-binding unit is accompanied by a change from dominant C–F...F–C and C–F...H–C contacts to π-stacking of arene domains between ligands 3 or 4.

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