Incommensurate phase in Λ-cobalt (III) sepulchrate trinitrate governed by highly competitive N-H...O and C-H...O hydrogen bond networks
- Phase transitions in molecular crystals are often determined by intermolecular interactions. The cage complex of [Co(C12H30N8)](3+) . 3 NO3- is reported to undergo a disorder-order phase transition at T-c1 approximate to 133 K upon cooling. Temperature-dependent neutron and synchrotron diffraction experiments revealed satellite reflections in addition to main reflections in the diffraction patterns below T-c1. The modulation wave vector varies as function of temperature and locks in at T-c3 approximate to 98 K. Here, we demonstrate that the crystal symmetry lowers from hexagonal to monoclinic in the incommensurately modulated phases in T-c1<T<T-c3. Distinctive levels of competitions: trade-off between longer N-H...O and shorter C-H...O hydrogen bonds; steric constraints to dense C-H...O bonds give rise to pronounced modulation of the basic structure. Severely frustrated crystal packing in the incommensurate phase is precursor to optimal balance of intermolecular interactions in the lock-in phase.
Author details: | Somnath DeyORCiD, Andreas SchönleberORCiDGND, Sander van SmaalenORCiDGND, Wolfgang MorgenrothORCiDGND, Finn Krebs Larsen |
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DOI: | https://doi.org/10.1002/chem.202104151 |
ISSN: | 0947-6539 |
ISSN: | 1521-3765 |
Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/35072296 |
Title of parent work (English): | Chemistry - a European journal |
Publisher: | Wiley-VCH |
Place of publishing: | Weinheim |
Publication type: | Article |
Language: | English |
Date of first publication: | 2022/01/24 |
Publication year: | 2022 |
Release date: | 2024/05/06 |
Tag: | hydrogen bond; incommensurate modulation; phase transition; steric factors; twin domains |
Volume: | 28 |
Issue: | 13 |
Article number: | e202104151 |
Number of pages: | 8 |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Geowissenschaften |
DDC classification: | 5 Naturwissenschaften und Mathematik / 55 Geowissenschaften, Geologie / 550 Geowissenschaften |
Peer review: | Referiert |
Publishing method: | Open Access / Hybrid Open-Access |
License (German): | CC-BY - Namensnennung 4.0 International |