Issue 17, 2021

Spodium bonding in five coordinated Zn(ii): a new player in crystal engineering?

Abstract

This manuscript evidences the existence and importance of spodium bonds (SpB) in solid state structures involving five-coordinated square-pyramidal Zn(II) spodium atoms. Four families of compounds have been found analysing the Cambridge structural database (CSD) where the interaction is very important to understand the crystal packing: (i) multi-dentate Schiff-base complexes, (ii) Zn-porphyrins, (iii) aza-crown ethers and (iv) polyoxometalates, the latter as SpB acceptors. The square-pyramidal around the metal center facilitates the approximation of the electron rich atom (ElR) to the Zn(II), contrariwise to the four-coordinated tetrahedral geometry where the steric crowd of the Zn ligands usually impedes the formation of the SpB. This highlight concentrates on the SpB interaction, which is different from the classical coordination bond in the sense that Y–Sp⋯A distances are longer (around the sum of van der Waals radii), the interaction weaker and it involves the σ* orbital of the Y–Sp bond (Y = any atom). A theoretical study on one representative family of compounds (Zn-porphyrins) has been also carried out indicating that the SpB energies range from −1 to −7.4 kcal mol−1. Finally, a statistical analysis of the CSD evidences that the interaction can be somewhat directional.

Graphical abstract: Spodium bonding in five coordinated Zn(ii): a new player in crystal engineering?

Supplementary files

Article information

Article type
Highlight
Submitted
15 ፌብሩ 2021
Accepted
04 ኤፕሪ 2021
First published
05 ኤፕሪ 2021

CrystEngComm, 2021,23, 3084-3093

Spodium bonding in five coordinated Zn(II): a new player in crystal engineering?

R. M. Gomila, A. Bauzá, T. J. Mooibroek and A. Frontera, CrystEngComm, 2021, 23, 3084 DOI: 10.1039/D1CE00221J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements