Next Article in Journal
Multicomponent Hosomi–Sakurai Reaction on Isosorbide Derivatives
Previous Article in Journal
Relationship Between Chemical Structures of Phytochemicals, Synthetic Phytochemical Analogs, and Antibiotics and Their In Vitro Growth-Inhibitory Effects Against Colorectal Cancer-Causing Bacteria
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Molecules
Volume 31
Issue 12
10.3390/molecules31122153
molecules-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
This is an early access version, the complete PDF, HTML, and XML versions will be available soon.
Article

Halogen Bonds or Not? Reassessing Noncovalent Interactions in Crystals of Periodate Anion from the Cambridge Structural Database

by
Arpita Varadwaj
1,*,
Pradeep R. Varadwaj
1,2,3,*,
Helder M. Marques
3,
Ireneusz Grabowski
2,4,
Koichi Yamashita
1 and
Mohd. Mudassir Husain
5
1
Department of Chemical System Engineering, School of Engineering, University of Tokyo, 7-3-1, Tokyo 113-8656, Japan
2
Institute of Physics, Faculty of Physics, Astronomy, and Informatics, Nicolaus Copernicus University in Toruń, 87-100 Toruń, Poland
3
Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg 2050, South Africa
4
Institute of Advanced Studies, Nicolaus Copernicus University in Toruń, Ul. Wileńska 4, 87-100 Toruń, Poland
5
Department of Applied Sciences and Humanities, Faculty of Engineering and Technology, Jamia Millia Islamia, New Delhi 110025, India
*
Authors to whom correspondence should be addressed.
Molecules 2026, 31(12), 2153; https://doi.org/10.3390/molecules31122153
Submission received: 22 May 2026 / Revised: 3 June 2026 / Accepted: 8 June 2026 / Published: 18 June 2026
(This article belongs to the Section Computational and Theoretical Chemistry)
Browse Figure
Versions Notes

Abstract

This study examines a series of organic–inorganic crystal structures containing the periodate anion (IO4−) to clarify the nature of the anion–anion interactions that are frequently referred to as halogen bonds. Our analysis demonstrates that, in many cases, IO4− does not develop an electrophilic σ-hole on the iodine center, even in the presence of organic cations, and therefore cannot reliably function as a halogen-bond donor. In its discrete (0D) form, the anion retains its character as a Lewis base. In crystal structures where extended architectures are observed—such as one-dimensional chains, two-dimensional layers, or three-dimensional cage-like assemblies—these structures arise predominantly from strong coulombic interactions with surrounding cations, as the interaction between the anions is intrinsically repulsive in the gas phase. Hydrogen bonding, together with other noncovalent interactions including chalcogen, tetrel, and/or pnictogen bonding, plays a dominant role in stabilizing the anionic arrangements and governing their structural organization.
Keywords: anion–anion non-covalent interactions; halogen-centered directional interactions; σ-hole centered interactions; physical chemistry and chemical physics; MESP; QTAIM; IGMH and SAPT analyses; interaction topology; crystallography; environmental effects anion–anion non-covalent interactions; halogen-centered directional interactions; σ-hole centered interactions; physical chemistry and chemical physics; MESP; QTAIM; IGMH and SAPT analyses; interaction topology; crystallography; environmental effects
Graphical Abstract

Share and Cite

MDPI and ACS Style

Varadwaj, A.; Varadwaj, P.R.; Marques, H.M.; Grabowski, I.; Yamashita, K.; Husain, M.M. Halogen Bonds or Not? Reassessing Noncovalent Interactions in Crystals of Periodate Anion from the Cambridge Structural Database. Molecules 2026, 31, 2153. https://doi.org/10.3390/molecules31122153

AMA Style

Varadwaj A, Varadwaj PR, Marques HM, Grabowski I, Yamashita K, Husain MM. Halogen Bonds or Not? Reassessing Noncovalent Interactions in Crystals of Periodate Anion from the Cambridge Structural Database. Molecules. 2026; 31(12):2153. https://doi.org/10.3390/molecules31122153

Chicago/Turabian Style

Varadwaj, Arpita, Pradeep R. Varadwaj, Helder M. Marques, Ireneusz Grabowski, Koichi Yamashita, and Mohd. Mudassir Husain. 2026. "Halogen Bonds or Not? Reassessing Noncovalent Interactions in Crystals of Periodate Anion from the Cambridge Structural Database" Molecules 31, no. 12: 2153. https://doi.org/10.3390/molecules31122153

APA Style

Varadwaj, A., Varadwaj, P. R., Marques, H. M., Grabowski, I., Yamashita, K., & Husain, M. M. (2026). Halogen Bonds or Not? Reassessing Noncovalent Interactions in Crystals of Periodate Anion from the Cambridge Structural Database. Molecules, 31(12), 2153. https://doi.org/10.3390/molecules31122153

Article Metrics

Back to TopTop