A1 Journal article (refereed)
N−X···O−N Halogen Bonds in Complexes of N‐Haloimides and Pyridine‐N‐oxides : A Large Data Set Study (2023)

Puttreddy, R., Rautiainen, M., Yu, S., & Rissanen, K. (2023). N−X···O−N Halogen Bonds in Complexes of N‐Haloimides and Pyridine‐N‐oxides : A Large Data Set Study. Angewandte Chemie, 62(34), Article e202307372. https://doi.org/10.1002/anie.202307372

JYU authors or editors

Publication details

All authors or editorsPuttreddy, Rakesh; Rautiainen, Mikko; Yu, Shilin; Rissanen, Kari

Journal or seriesAngewandte Chemie



Publication year2023

Publication date14/06/2023


Issue number34

Article numbere202307372


Publication countryGermany

Publication languageEnglish


Publication open accessOpenly available

Publication channel open accessPartially open access channel

Publication is parallel published (JYX)https://jyx.jyu.fi/handle/123456789/88952


N–X···−O–N+ halogen-bonded systems formed by 27 pyridine N-oxides (PyNOs) as halogen bond (XB) acceptors and two N-halosuccinimides, two N-halophthalimides, and two N-halosaccharins as XB donors are studied in silico, in solution, and in the solid state. This large set of data (132 DFT optimized structures, 75 crystal structures, and 168 1H NMR titrations) provides a unique view to structural and bonding properties. In the computational part, a simple electrostatic model (SiElMo) for predicting XB energies using only the properties of halogen donors and oxygen acceptors is developed. The SiElMo energies are in perfect accord with energies calculated from XB complexes optimized with two high-level DFT approaches. Data from in silico bond energies and single crystal X-ray structures correlate, however data from solution do not. The polydentate bonding characteristic of the PyNOs’ oxygen in solution, as revealed by solid-state structures, is attributed to the lack of correlation between DFT/solid-state and solution data. XB strength is only slightly affected by the PyNO oxygen properties [(atomic charge (Q), ionization energy (Is,min) and local negative minima (Vs,min)], as the 𝜎-hole (Vs,max) of the donor halogen is the key determinant leading to the sequence N-halosaccharin>N-halosuccinimide> N-halophthalimide on the XB strength.

Keywordschemical bondscoordination complexesdensity functional theory

Free keywordshalogen bond; N-oxide; N-Haloimide; DFT; X-ray structure

Contributing organizations

Related projects

Ministry reportingYes

Reporting Year2023

Preliminary JUFO rating3

Last updated on 2024-18-02 at 19:27