Reversible phase transition in 8,19-dimethyl-2,3,8,19-tetraazapentacyclo[13.7.0.04,12.06,10.017,21]docosa-1(15),2,4(12),5,10,16,21-heptaene-7,9,18,20-tetrone

The crystal structure of the title compound, C20H14N4O4, was previously reported at 220 K [Businski et al. (2025). Chem. Eur. J. A71, 3–8], where it crystallizes in the monoclinic space group P21/c with one crystallographically independent molecule in a general position. In this structure, disorder...

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Main Authors: Christian Näther, Artjom Businski, Rainer Herges
Format: Article
Language:English
Published: International Union of Crystallography 2025-06-01
Series:Acta Crystallographica Section E: Crystallographic Communications
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Online Access:https://journals.iucr.org/paper?S2056989025003998
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author Christian Näther
Artjom Businski
Rainer Herges
author_facet Christian Näther
Artjom Businski
Rainer Herges
author_sort Christian Näther
collection DOAJ
description The crystal structure of the title compound, C20H14N4O4, was previously reported at 220 K [Businski et al. (2025). Chem. Eur. J. A71, 3–8], where it crystallizes in the monoclinic space group P21/c with one crystallographically independent molecule in a general position. In this structure, disorder of the methyl H atoms is observed. However, upon cooling a continuous splitting of the reflections occurs, that might indicate a phase transition. Therefore, data sets were measured between room temperature and 90 K upon cooling and reheating, which shows that a discontinuity in the unit-cell volume occurs between 170 and 180 K. This process is accompanied by the formation of an additional crystal domain. Both domains can be indexed separately, leading to a unit cell similar to that observed at room temperature, but with both α and β angles revealing significant deviations from 90°. Twin refinements clearly show that the structure becomes triclinic (space group P1) upon cooling, resulting in two crystallographically independent molecules in the unit cell, for which some structural changes especially in the conformation and arrangement of the molecules are observed. In the low-temperature structure, disordering of the methyl H atoms is still observed. If the crystal is reheated, the reflections of the second domain disappear and the structure can be successfully refined again in the monoclinic space group P21/c, indicating reversibility of the transition.
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spelling doaj-art-80d548c1758940d7af600c22a2c55fdc2025-08-20T03:26:43ZengInternational Union of CrystallographyActa Crystallographica Section E: Crystallographic Communications2056-98902025-06-0181647648110.1107/S2056989025003998hb8139Reversible phase transition in 8,19-dimethyl-2,3,8,19-tetraazapentacyclo[13.7.0.04,12.06,10.017,21]docosa-1(15),2,4(12),5,10,16,21-heptaene-7,9,18,20-tetroneChristian Näther0Artjom Businski1Rainer Herges2Institut für Anorganische Chemie, Universität Kiel, GermanyOtto-Diels-Institut für Organische Chemie, Universität Kiel, GermanyOtto-Diels-Institut für Organische Chemie, Universität Kiel, GermanyThe crystal structure of the title compound, C20H14N4O4, was previously reported at 220 K [Businski et al. (2025). Chem. Eur. J. A71, 3–8], where it crystallizes in the monoclinic space group P21/c with one crystallographically independent molecule in a general position. In this structure, disorder of the methyl H atoms is observed. However, upon cooling a continuous splitting of the reflections occurs, that might indicate a phase transition. Therefore, data sets were measured between room temperature and 90 K upon cooling and reheating, which shows that a discontinuity in the unit-cell volume occurs between 170 and 180 K. This process is accompanied by the formation of an additional crystal domain. Both domains can be indexed separately, leading to a unit cell similar to that observed at room temperature, but with both α and β angles revealing significant deviations from 90°. Twin refinements clearly show that the structure becomes triclinic (space group P1) upon cooling, resulting in two crystallographically independent molecules in the unit cell, for which some structural changes especially in the conformation and arrangement of the molecules are observed. In the low-temperature structure, disordering of the methyl H atoms is still observed. If the crystal is reheated, the reflections of the second domain disappear and the structure can be successfully refined again in the monoclinic space group P21/c, indicating reversibility of the transition.https://journals.iucr.org/paper?S2056989025003998diazocinephotoswitchphase transitionreversibilitytemperature-dependent measurementstwinningcrystal structure
spellingShingle Christian Näther
Artjom Businski
Rainer Herges
Reversible phase transition in 8,19-dimethyl-2,3,8,19-tetraazapentacyclo[13.7.0.04,12.06,10.017,21]docosa-1(15),2,4(12),5,10,16,21-heptaene-7,9,18,20-tetrone
Acta Crystallographica Section E: Crystallographic Communications
diazocine
photoswitch
phase transition
reversibility
temperature-dependent measurements
twinning
crystal structure
title Reversible phase transition in 8,19-dimethyl-2,3,8,19-tetraazapentacyclo[13.7.0.04,12.06,10.017,21]docosa-1(15),2,4(12),5,10,16,21-heptaene-7,9,18,20-tetrone
title_full Reversible phase transition in 8,19-dimethyl-2,3,8,19-tetraazapentacyclo[13.7.0.04,12.06,10.017,21]docosa-1(15),2,4(12),5,10,16,21-heptaene-7,9,18,20-tetrone
title_fullStr Reversible phase transition in 8,19-dimethyl-2,3,8,19-tetraazapentacyclo[13.7.0.04,12.06,10.017,21]docosa-1(15),2,4(12),5,10,16,21-heptaene-7,9,18,20-tetrone
title_full_unstemmed Reversible phase transition in 8,19-dimethyl-2,3,8,19-tetraazapentacyclo[13.7.0.04,12.06,10.017,21]docosa-1(15),2,4(12),5,10,16,21-heptaene-7,9,18,20-tetrone
title_short Reversible phase transition in 8,19-dimethyl-2,3,8,19-tetraazapentacyclo[13.7.0.04,12.06,10.017,21]docosa-1(15),2,4(12),5,10,16,21-heptaene-7,9,18,20-tetrone
title_sort reversible phase transition in 8 19 dimethyl 2 3 8 19 tetraazapentacyclo 13 7 0 04 12 06 10 017 21 docosa 1 15 2 4 12 5 10 16 21 heptaene 7 9 18 20 tetrone
topic diazocine
photoswitch
phase transition
reversibility
temperature-dependent measurements
twinning
crystal structure
url https://journals.iucr.org/paper?S2056989025003998
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AT artjombusinski reversiblephasetransitionin819dimethyl23819tetraazapentacyclo13700412061001721docosa11524125101621heptaene791820tetrone
AT rainerherges reversiblephasetransitionin819dimethyl23819tetraazapentacyclo13700412061001721docosa11524125101621heptaene791820tetrone