The University of Southampton
University of Southampton Institutional Repository

Co-crystallisation of cytosine with 1,10-phenanthroline: computational screening and experimental realisation

Co-crystallisation of cytosine with 1,10-phenanthroline: computational screening and experimental realisation
Co-crystallisation of cytosine with 1,10-phenanthroline: computational screening and experimental realisation
Attempts to co-crystallise the nucleobases adenine, thymine, guanine, and cytosine with 1,10-phenanthroline by ball milling and solvent evaporation methods are described. A 1 : 1 co-crystal of cytosine and 1,10-phenanthroline can be obtained by grinding or by solvent evaporation. The structure contains two crystallographically independent cytosine and two independent 1,10-phenanthroline molecules (Z? = 2). The cytosine molecules form two similar but crystallographically independent hydrogen-bonded chains, while the 1,10-phenanthroline molecules are arranged in ?-stacks. Between the chains of cytosine and the ?-stacks exist N–H?N and C–H?N interactions. Crystal structure prediction (CSP) calculations were applied to all four systems to assess their potential for co-crystallisation as well as the likely structures and intermolecular interactions that could result from co-crystallisation. Calculations on the cytosine system demonstrate that co-crystallisation results in a lower energy than the crystalline forms of the two starting materials, in line with the co-crystal formation observed. For the systems which did not form a co-crystal, CSP was used to explore potential packing arrangements, but found none which were lower in energy than that of the pure crystalline forms. In these cases there is significant disruption to the nucleobase hydrogen bonding between the pure compound and the hypothetical co-crystal. For pure adenine and guanine, the hydrogen-bonded ribbons form sheets which must be broken, whereas for thymine, the lack of hydrogen bond donors does not allow the hydrogen bonding present for pure thymine to be maintained while forming thymine-1,10-phenanthroline hydrogen bonds.
1466-8033
7130-7141
Hoxha, Kreshnik
e15e8bb1-ab18-4aa2-935b-818e5df4b873
Case, David H.
5697af1e-06b6-4e46-83eb-185cec9699ec
Day, Graeme M.
e3be79ba-ad12-4461-b735-74d5c4355636
Prior, Timothy J.
8224d02f-3cb2-4dd5-87d4-9850c5e06796
Hoxha, Kreshnik
e15e8bb1-ab18-4aa2-935b-818e5df4b873
Case, David H.
5697af1e-06b6-4e46-83eb-185cec9699ec
Day, Graeme M.
e3be79ba-ad12-4461-b735-74d5c4355636
Prior, Timothy J.
8224d02f-3cb2-4dd5-87d4-9850c5e06796

Hoxha, Kreshnik, Case, David H., Day, Graeme M. and Prior, Timothy J. (2015) Co-crystallisation of cytosine with 1,10-phenanthroline: computational screening and experimental realisation. CrystEngComm, (37), 7130-7141. (doi:10.1039/c5ce01286d).

Record type: Article

Abstract

Attempts to co-crystallise the nucleobases adenine, thymine, guanine, and cytosine with 1,10-phenanthroline by ball milling and solvent evaporation methods are described. A 1 : 1 co-crystal of cytosine and 1,10-phenanthroline can be obtained by grinding or by solvent evaporation. The structure contains two crystallographically independent cytosine and two independent 1,10-phenanthroline molecules (Z? = 2). The cytosine molecules form two similar but crystallographically independent hydrogen-bonded chains, while the 1,10-phenanthroline molecules are arranged in ?-stacks. Between the chains of cytosine and the ?-stacks exist N–H?N and C–H?N interactions. Crystal structure prediction (CSP) calculations were applied to all four systems to assess their potential for co-crystallisation as well as the likely structures and intermolecular interactions that could result from co-crystallisation. Calculations on the cytosine system demonstrate that co-crystallisation results in a lower energy than the crystalline forms of the two starting materials, in line with the co-crystal formation observed. For the systems which did not form a co-crystal, CSP was used to explore potential packing arrangements, but found none which were lower in energy than that of the pure crystalline forms. In these cases there is significant disruption to the nucleobase hydrogen bonding between the pure compound and the hypothetical co-crystal. For pure adenine and guanine, the hydrogen-bonded ribbons form sheets which must be broken, whereas for thymine, the lack of hydrogen bond donors does not allow the hydrogen bonding present for pure thymine to be maintained while forming thymine-1,10-phenanthroline hydrogen bonds.

Text
s1-ln210949871007204532-1939656818Hwf-1909625263IdV-93119064721094987PDF_HI0001.pdf - Accepted Manuscript
Available under License Other.
Download (2MB)
Text
CEC2015_phen_nucleobase_cocrystals.pdf - Version of Record
Available under License Other.
Download (4MB)

More information

Accepted/In Press date: 12 August 2015
e-pub ahead of print date: 12 August 2015
Organisations: Chemistry, Computational Systems Chemistry

Identifiers

Local EPrints ID: 380765
URI: http://eprints.soton.ac.uk/id/eprint/380765
ISSN: 1466-8033
PURE UUID: 9e8d6dd0-1df6-414f-9875-bad857f153d4
ORCID for Graeme M. Day: ORCID iD orcid.org/0000-0001-8396-2771

Catalogue record

Date deposited: 17 Sep 2015 12:49
Last modified: 26 Nov 2019 01:37

Export record

Altmetrics

Contributors

Author: Kreshnik Hoxha
Author: David H. Case
Author: Graeme M. Day ORCID iD
Author: Timothy J. Prior

University divisions

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×