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Analysis of ion-ion interactions in the crystal structure of triazaphenalenium hexahydropyrimidopyrimidinium bistosylate

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Abstract

The solid-state structure of triazaphenalenium hexahydropyrimidopyrimidinium bistosylate has been determined by single-crystal X-ray crystallography (Cc, Z = 4, a = 8.407(2) Å, b = 8.407(2) Å, c = 25.678(6) Å, β = 92.610(4)°, R1 = 0.0583), marking the first time that a tricyclic guanidinium-type carbocation has been structurally characterized. The orthoamide moiety in the triazaphenalenium ion was planar, and density functional theory calculations on the free triazaphenalenium ion indicated that the central carbon was the locus of positive charge in this ion. Hirshfeld surfaces and fingerprint plots of the packing in this structure revealed numerous weak (e.g., C-H···O, C-H···π) interactions among the ions in the compound. These ions were arranged in columns, each consisting of tosylate ions interdigitated with either triazaphenalenium or hexahydropyrimidopyrimidinium ions. These columns were linked by N–H···O hydrogen bonds between the hexahydropyrimidopyrimidinium moiety in one column and one of the two tosylates in a neighboring column. The net result of these packing forces was a layering of these columns in the bulk, with a polar (sulfonate-dominated) surface on one face of each layer and a nonpolar (methylene-dominated) surface on the opposite face.

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Data availability

The CIF file for compound 2 in the manuscript has been deposited with the Cambridge Crystallographic Data Centre with the deposition number 2312982. Additional data is provided with the Supplementary Information file.

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Funding

AL and ATR acknowledge funding support from the University of West Florida through faculty startup funds, Office of Undergraduate Research project awards and student stipend support from the SURP program to CP. PB and NVM gratefully acknowledge the support of the National Research, Development and Innovation Fund NKFIA (Hungary) through project OTKA K-124544.

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Authors and Affiliations

  1. Department of Chemistry, University of West Florida, 11000 University Parkway, Pensacola, FL, 32514, USA

    A. Timothy Royappa, Christina V. Pizza & Ajay Lajmi

  2. Research Laboratory of Chemical Crystallography, Centre for Structural Science, Research Centre for Natural Sciences, Magyar Tudósok Körútja 2, 1117, Budapest, Hungary

    Petra Bombicz & Nóra V. May

  3. Department of Chemistry, University of California San Diego, La Jolla, CA, 92093, USA

    Arnold L. Rheingold

Authors
  1. A. Timothy Royappa
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  2. Petra Bombicz
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  3. Nóra V. May
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  4. Christina V. Pizza
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  5. Arnold L. Rheingold
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  6. Ajay Lajmi
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Contributions

AL designed and supervised the synthesis and reviewed the manuscript; CVP carried out the synthesis and spectroscopic analysis; ATR performed the crystallization and computational studies and wrote the manuscript; ALR obtained the crystal structure; PB and NVM completed the structural analysis and reviewed the manuscript.

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Correspondence to A. Timothy Royappa.

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Supplementary file1 (DOCX 455 KB)

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Royappa, A.T., Bombicz, P., May, N.V. et al. Analysis of ion-ion interactions in the crystal structure of triazaphenalenium hexahydropyrimidopyrimidinium bistosylate. Struct Chem (2024). https://doi.org/10.1007/s11224-023-02274-1

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  • DOI: https://doi.org/10.1007/s11224-023-02274-1

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