Aromatic hexazine [N6]4- anion featured in the complex structure of the high-pressure potassium nitrogen compound K9N56

doi:10.1038/s41557-023-01148-7

. 2023 May;15(5):641-646.

doi: 10.1038/s41557-023-01148-7. Epub 2023 Mar 6.

Aromatic hexazine [N₆]^4- anion featured in the complex structure of the high-pressure potassium nitrogen compound K₉N₅₆

Dominique Laniel^{1

2}, Florian Trybel³, Yuqing Yin^{4

5}, Timofey Fedotenko⁴, Saiana Khandarkhaeva⁶, Andrey Aslandukov⁴, Georgios Aprilis⁷, Alexei I Abrikosov⁸, Talha Bin Masood⁸, Carlotta Giacobbe⁷, Eleanor Lawrence Bright⁷, Konstantin Glazyrin⁹, Michael Hanfland⁷, Jonathan Wright⁷, Ingrid Hotz⁸, Igor A Abrikosov³, Leonid Dubrovinsky⁵, Natalia Dubrovinskaia^{4

3}

Affiliations

¹ Material Physics and Technology at Extreme Conditions, Laboratory of Crystallography, University of Bayreuth, Bayreuth, Germany. dominique.laniel@ed.ac.uk.
² Centre for Science at Extreme Conditions and School of Physics and Astronomy, University of Edinburgh, Edinburgh, UK. dominique.laniel@ed.ac.uk.
³ Department of Physics, Chemistry and Biology (IFM), Linköping University, Linköping, Sweden.
⁴ Material Physics and Technology at Extreme Conditions, Laboratory of Crystallography, University of Bayreuth, Bayreuth, Germany.
⁵ State Key Laboratory of Crystal Materials, Shandong University, Jinan, China.
⁶ Bayerisches Geoinstitut, University of Bayreuth, Bayreuth, Germany.
⁷ European Synchrotron Radiation Facility, Grenoble, France.
⁸ Department of Science and Technology (ITN), Linköping University, Norrköping, Sweden.
⁹ Photon Science, Deutsches Elektronen-Synchrotron, Hamburg, Germany.

PMID: 36879075
DOI: 10.1038/s41557-023-01148-7

Aromatic hexazine [N₆]^4- anion featured in the complex structure of the high-pressure potassium nitrogen compound K₉N₅₆

Dominique Laniel et al. Nat Chem. 2023 May.

. 2023 May;15(5):641-646.

doi: 10.1038/s41557-023-01148-7. Epub 2023 Mar 6.

Authors

Affiliations

¹ Material Physics and Technology at Extreme Conditions, Laboratory of Crystallography, University of Bayreuth, Bayreuth, Germany. dominique.laniel@ed.ac.uk.
² Centre for Science at Extreme Conditions and School of Physics and Astronomy, University of Edinburgh, Edinburgh, UK. dominique.laniel@ed.ac.uk.
³ Department of Physics, Chemistry and Biology (IFM), Linköping University, Linköping, Sweden.
⁴ Material Physics and Technology at Extreme Conditions, Laboratory of Crystallography, University of Bayreuth, Bayreuth, Germany.
⁵ State Key Laboratory of Crystal Materials, Shandong University, Jinan, China.
⁶ Bayerisches Geoinstitut, University of Bayreuth, Bayreuth, Germany.
⁷ European Synchrotron Radiation Facility, Grenoble, France.
⁸ Department of Science and Technology (ITN), Linköping University, Norrköping, Sweden.
⁹ Photon Science, Deutsches Elektronen-Synchrotron, Hamburg, Germany.

PMID: 36879075
DOI: 10.1038/s41557-023-01148-7

Abstract

The recent high-pressure synthesis of pentazolates and the subsequent stabilization of the aromatic [N₅]^- anion at atmospheric pressure have had an immense impact on nitrogen chemistry. Other aromatic nitrogen species have also been actively sought, including the hexaazabenzene N₆ ring. Although a variety of configurations and geometries have been proposed based on ab initio calculations, one that stands out as a likely candidate is the aromatic hexazine anion [N₆]^4-. Here we present the synthesis of this species, realized in the high-pressure potassium nitrogen compound K₉N₅₆ formed at high pressures (46 and 61 GPa) and high temperature (estimated to be above 2,000 K) by direct reaction between nitrogen and KN₃ in a laser-heated diamond anvil cell. The complex structure of K₉N₅₆-composed of 520 atoms per unit cell-was solved based on synchrotron single-crystal X-ray diffraction and corroborated by density functional theory calculations. The observed hexazine anion [N₆]^4- is planar and proposed to be aromatic.

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References

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[1] von Schleyer, P. R. & Jiao, H. What is aromaticity? Pure Appl. Chem. 68, 209–218 (1996). - DOI

[2] von Schleyer, P. R. & Jiao, H. What is aromaticity? Pure Appl. Chem. 68, 209–218 (1996). - DOI

[3] Cook, M. J., Katritzky, A. R. & Linda, P. Aromaticity of heterocycles. In Advances in Heterocyclic Chemistry 255–356 (1974); https://doi.org/10.1016/S0065-2725(08)60910-1

[4] Cook, M. J., Katritzky, A. R. & Linda, P. Aromaticity of heterocycles. In Advances in Heterocyclic Chemistry 255–356 (1974); https://doi.org/10.1016/S0065-2725(08)60910-1

[5] Krygowski, T. M. & Szatylowicz, H. Aromaticity: what does it mean? ChemTexts 1, 12 (2015). - PubMed - PMC - DOI

[6] Krygowski, T. M. & Szatylowicz, H. Aromaticity: what does it mean? ChemTexts 1, 12 (2015). - PubMed - PMC - DOI

[7] Kaneda, H., Onaka, T. & Sakon, I. Detection of PAH emission features from nearby elliptical galaxies with the Spitzer infrared spectrograph. Astrophys. J. 632, L83–L86 (2005). - DOI

[8] Kaneda, H., Onaka, T. & Sakon, I. Detection of PAH emission features from nearby elliptical galaxies with the Spitzer infrared spectrograph. Astrophys. J. 632, L83–L86 (2005). - DOI

[9] Cruikshank, D. P., Dalle Ore, C. M., Clark, R. N. & Pendleton, Y. J. Aromatic and aliphatic organic materials on Iapetus: analysis of Cassini VIMS data. Icarus 233, 306–315 (2014). - DOI

[10] Cruikshank, D. P., Dalle Ore, C. M., Clark, R. N. & Pendleton, Y. J. Aromatic and aliphatic organic materials on Iapetus: analysis of Cassini VIMS data. Icarus 233, 306–315 (2014). - DOI

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Aromatic hexazine [N₆]^4- anion featured in the complex structure of the high-pressure potassium nitrogen compound K₉N₅₆

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Aromatic hexazine [N₆]^4- anion featured in the complex structure of the high-pressure potassium nitrogen compound K₉N₅₆

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