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Modelling of crystal structure of cis-1,2,3,6 and 3,4,5,6-tetrahydrophthalic anhydrides using lattice energy calculations

Modelling of crystal structure of cis-1,2,3,6 and 3,4,5,6-tetrahydrophthalic anhydrides using lattice energy calculations
Modelling of crystal structure of cis-1,2,3,6 and 3,4,5,6-tetrahydrophthalic anhydrides using lattice energy calculations
Lattice energy calculations using a model potential were performed to model the crystal structures of cis-1,2,3,6- and 3,4,5,6-tetrahydrophthalic (THP) anhydrides. The optimized molecular models using the DFT method at the B3LYP/6-31G** level were found consistent with the available experimental evidence and allowed all differences observed in crystal packing between cis-1,2,3,6- and 3,4,5,6-THP anhydrides to be reproduced. Calculations provide evidence for the presence of dipole–dipole C=O?C=O intermolecular interactions and support the idea that the molecules distort from their ideal geometries, improving packing in both crystals. The search for minima in the lattice energy of both crystals amongst the more common space groups with Z’?=?1, using a simulated annealing crystal structure prediction procedure followed by lattice energy minimization showed that the observed structure of 3,4,5,6-THP anhydride (Z’?=?2) is the thermodynamically most stable, and allowed us to justify why 3,4,5,6-THP anhydride crystallizes in such a complex structure with 16 molecules in the unit cell. The computational model was successful in predicting the second observed form at 173 K for cis-1,2,3,6-THP anhydride as a polymorph, and could predict several hypothetical structures with Z’?=?1 that appear competitive with the observed structures. The results of phonon estimates of zero point intermolecular vibrational energy and entropy suggest that crystal structures of cis-1,2,3,6-THP anhydride cannot be predicted solely on the basis of lattice energy; factors other than thermodynamics favor the observed structures.
anhydride, crystal structure prediction, lattice energy calculation, intermolecular interaction
1610-2940
1-14
Fredj, Arij Ben
5aaa9270-f30f-4dbb-8c64-4047f4e3e667
Day, Graeme
e3be79ba-ad12-4461-b735-74d5c4355636
Fredj, Arij Ben
5aaa9270-f30f-4dbb-8c64-4047f4e3e667
Day, Graeme
e3be79ba-ad12-4461-b735-74d5c4355636

Fredj, Arij Ben and Day, Graeme (2015) Modelling of crystal structure of cis-1,2,3,6 and 3,4,5,6-tetrahydrophthalic anhydrides using lattice energy calculations. Journal of Molecular Modeling, 21 (211), 1-14. (doi:10.1007/s00894-015-2756-4).

Record type: Article

Abstract

Lattice energy calculations using a model potential were performed to model the crystal structures of cis-1,2,3,6- and 3,4,5,6-tetrahydrophthalic (THP) anhydrides. The optimized molecular models using the DFT method at the B3LYP/6-31G** level were found consistent with the available experimental evidence and allowed all differences observed in crystal packing between cis-1,2,3,6- and 3,4,5,6-THP anhydrides to be reproduced. Calculations provide evidence for the presence of dipole–dipole C=O?C=O intermolecular interactions and support the idea that the molecules distort from their ideal geometries, improving packing in both crystals. The search for minima in the lattice energy of both crystals amongst the more common space groups with Z’?=?1, using a simulated annealing crystal structure prediction procedure followed by lattice energy minimization showed that the observed structure of 3,4,5,6-THP anhydride (Z’?=?2) is the thermodynamically most stable, and allowed us to justify why 3,4,5,6-THP anhydride crystallizes in such a complex structure with 16 molecules in the unit cell. The computational model was successful in predicting the second observed form at 173 K for cis-1,2,3,6-THP anhydride as a polymorph, and could predict several hypothetical structures with Z’?=?1 that appear competitive with the observed structures. The results of phonon estimates of zero point intermolecular vibrational energy and entropy suggest that crystal structures of cis-1,2,3,6-THP anhydride cannot be predicted solely on the basis of lattice energy; factors other than thermodynamics favor the observed structures.

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Accepted/In Press date: 6 July 2015
e-pub ahead of print date: 30 July 2015
Published date: August 2015
Keywords: anhydride, crystal structure prediction, lattice energy calculation, intermolecular interaction
Organisations: Chemistry

Identifiers

Local EPrints ID: 389697
URI: http://eprints.soton.ac.uk/id/eprint/389697
ISSN: 1610-2940
PURE UUID: b5fc53e5-a32a-4bcc-9c8c-49ba05bb3ebe
ORCID for Graeme Day: ORCID iD orcid.org/0000-0001-8396-2771

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Date deposited: 14 Mar 2016 10:28
Last modified: 20 Jul 2019 00:41

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Author: Arij Ben Fredj
Author: Graeme Day ORCID iD

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