CrystEngComm Blog

Crystal growth of aniline-II at 0.8 GPa

In an extension to previous work showing that H-bond lengths are pressure sensitive, Parsons and co-workers used the PIXEL method (a computational method for structural prediction) to study the variation in energy of intermolecular interactions with pressure, in two crystalline phases of aniline.  

For aniline II, at a pressure of 7.3 GPa, the pressure-induced shortening of the H-bonds was found to go beyond the Cambridge Structural Database limit with the H-bonds being similar in energy to the CH-π contacts.

This ability to manipulate the hierarchy of intermolecular interactions by high pressure could have potentially important implications in crystal engineering.

Read more for FREE about the use of high pressure in crystalline solids at:

Destabilisation of hydrogen bonding and the phase stability of aniline at high pressure
Nicholas P. Funnell, Alice Dawson, William G. Marshall and Simon Parsons
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C2CE26403J, Paper

You may also want to check out previous work from Simon Parsons:

Alanine at 13.6 GPa and its pressure-induced amorphisation at 15 GPa
Nicholas P. Funnell, William G. Marshall and Simon Parsons
CrystEngComm, 2011, 13, 5841-5848
DOI: 10.1039/C1CE05487B, Paper

The effect of pressure on the crystal structure of L-alanine
Nicholas P. Funnell, Alice Dawson, Duncan Francis, Alistair R. Lennie, William G. Marshall, Stephen A. Moggach, John E. Warren and Simon Parsons
CrystEngComm, 2010, 12, 2573-2583
DOI: 10.1039/C001296C, Paper

Robert LaDuca, and colleagues at Michigan State University, have hydrothermally synthesised divalent metal coordination polymers featuring the ligand, 3-pyridylisonicotinamide (3-pina).  The 3-pina ligand has a hydrogen bonding donor and acceptor locus at its central amide, making supramolecular structure direction achievable, something that is not possible using the regularly tested ligand, 4,4′-bipyridine.

The 3-pyridylisonicotinamide ligand has a kinked disposition of its nitrogen atoms.

The team discuss 3 very diverse structures featuring the 3-pina ligand, showing that the dimensionality in the resulting coordination polymers very much depends on the metal coordination environment and the sulfate binding mode that occurs in each case.

Download the paper now to find out more:

Metal dependent dimensionality in sulfate coordination polymers containing 3-pyridylisonicotinamide
Jacqueline S. Lucas, Jacob W. Uebler and Robert L. LaDuca
CrystEngComm, 2012
DOI: 10.1039/C2CE26333E, Paper

Take a look at some of the teams other recent CrystEngComm articles:

Topological diversity in zinc coordination polymers with 5-substituted isophthalate and bis(4-pyridylmethyl)piperazine ligands
Amy L. Pochodylo and Robert L. LaDuca
CrystEngComm, 2011,13, 2249-2261
DOI: 10.1039/C0CE00715C, Paper

Metal and ligand binding mode dependent topologies in phthalate coordination polymers with bis(4-pyridylformyl)piperazine co-ligands
Curtis Y. Wang, Zachary M. Wilseck, Ronald M. Supkowski and Robert L. LaDuca
CrystEngComm, 2011,13, 1391-1399
DOI: 10.1039/C0CE00632G, Paper

Cadmium bis(4-pyridylformyl)piperazine coordination polymers: layered nets and a novel 3,5-connected binodal lattice
Jacqueline S. Lucas, Amy L. Pochodylo and Robert L. LaDuca
CrystEngComm, 2010,12, 3310-3317
DOI: 10.1039/C0CE00117A, Paper

In their 2011, CrystEngComm article, the team reported on the development of a sulfonamidecinnamic acid framework which could be likened to the shape of a fish-hook. Upon crystallisation, the structures form supramolecular dimers where the neighbouring C=C double bonds are oriented mutally co-planar. It is this feature that allows UV initiated dimerisation into the corresponding cyclobutane product.

In their latest CrystEngComm, they extend this study by looking at a greater range of frameworks with different R substituents. To see what impact this has on the supramolecular photodimerisation, download the article now for FREE:

Solid-state photodimerization reactions of racemic and homochiral phenylalanine sulfonamidecinnamic acids
Zhiqing Yan, Andrew J. Bolokowicz, Teage K. Collett, Sarah A. Reeb, Joshua D. Wiseman and Kraig A. Wheeler
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C2CE26307F

Also of interest:
Enantiocontrolled solid-state photodimerizations via a chiral sulfonamidecinnamic acid
Kraig A. Wheeler, Joshua D. Wiseman and Rebecca C. Grove
CrystEngComm, 2011, 13, 3134–3137
DOI: 10.1039/C0CE00516A

In this HOT Article, Franca Jones suggests the existence of highly disordered clusters that form prior to crystallization of barite and gypsum, based on  Fourier-Transform infra-red (FTIR) spectra of saturated solutions as they crystallize.  Jones reports the  evolution of various mineral phases prior to the appearance of the crystalline mature product and in the case of barite, shows that the FTIR evidence is strongly supported by electron diffraction. The role of water in the process is also investigated…

Read more for FREE at: 

Infrared investigation of barite and gypsum crystallization: Evidence for an amorphous to crystalline transition
Franca Jones
CrystEngComm, 2012, Advance Article
DOI: 10.1039/C2CE25918D 

Also of interest may be: 

Barium sulfate crystallization dependence on upper rim calix[4]arene functional groups
Andrew Baynton, Mark I. Ogden, Colin L. Raston and Franca Jones
CrystEngComm, 2012, 14, 1057-1062
DOI: 10.1039/C1CE06083J