TY - JOUR

T1 - Structures and Chemical Bonding in Antimony(III) Bromide Complexes with Pyridine

AU - Prokudina, Yana V.

AU - Davydova, Elena I.

AU - Virovets, Alexander

AU - Stöger, Berthold

AU - Peresypkina, Eugenia

AU - Pomogaeva, Anna V.

AU - Timoshkin, Alexey Y.

N1 - Funding Information: Computational studies have been carried out using resources of the «Computing Center» of the Research park of St. Petersburg State University. X‐ray powder diffraction measurements were performed at the “Center for X‐ray Diffraction Studies” of the Research park of St. Petersburg State University. STA measurements were performed by Mikhail Chislov at the “Center for Thermogravimetric and Calorimetric Research” of the Research park of St. Petersburg State University. We thank Dmitry Zimin for his contribution to the synthesis of . We thank Prof. Manfred Scheer for the use of the diffractometer. We thank reviewers for helpful comments. Funding: This work was supported by the Russian Science Foundation grant number 18‐13‐00196. 1 Publisher Copyright: © 2020 Wiley-VCH GmbH Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/12/9

Y1 - 2020/12/9

N2 - Weakly or “partially” bonded molecules are an important link between the chemical and van der Waals interactions. Molecular structures of six new SbBr3-Py complexes in the solid state have been determined by single-crystal X-ray diffraction analysis. In all complexes all Sb atoms adopt a pseudo-octahedral coordination geometry which is completed by additional Sb⋅⋅⋅Br contacts shorter than the sum of the van der Waals radii, with Br−Sb⋅⋅⋅Br angles close to 180°. To reveal the nature of Sb–Br and Sb–N interactions, the DFT calculations were performed followed by the analysis of the electrostatic potentials, the orbital interactions and the topological analysis. Based on Natural Bond Orbital (NBO) analysis, the Sb–Br interactions range from the covalent bonds to the pnictogen bonds. A simple structural parameter, non-covalence criterion (NCC) is defined as a ratio of the atom-atom distance to the linear combination of sums of covalent and van der Waals radii. NCC correlates with E(2) values for Sb−N, Sb−Cl and Sb−Br bonds, and appears to be useful criterion for a preliminary evaluation of the bonding situation.

AB - Weakly or “partially” bonded molecules are an important link between the chemical and van der Waals interactions. Molecular structures of six new SbBr3-Py complexes in the solid state have been determined by single-crystal X-ray diffraction analysis. In all complexes all Sb atoms adopt a pseudo-octahedral coordination geometry which is completed by additional Sb⋅⋅⋅Br contacts shorter than the sum of the van der Waals radii, with Br−Sb⋅⋅⋅Br angles close to 180°. To reveal the nature of Sb–Br and Sb–N interactions, the DFT calculations were performed followed by the analysis of the electrostatic potentials, the orbital interactions and the topological analysis. Based on Natural Bond Orbital (NBO) analysis, the Sb–Br interactions range from the covalent bonds to the pnictogen bonds. A simple structural parameter, non-covalence criterion (NCC) is defined as a ratio of the atom-atom distance to the linear combination of sums of covalent and van der Waals radii. NCC correlates with E(2) values for Sb−N, Sb−Cl and Sb−Br bonds, and appears to be useful criterion for a preliminary evaluation of the bonding situation.

KW - antimony(III) complexes

KW - DFT computations

KW - electronic structure

KW - pnictogen bonds

KW - structural analysis

KW - COORDINATION CHEMISTRY

KW - ALKOXIDE CAGES

KW - CRYSTAL-STRUCTURES

KW - NONCOVALENT INTERACTIONS

KW - MAIN-GROUP ELEMENTS

KW - THERMAL-DECOMPOSITION

KW - SOLID-STATE

KW - PNICOGEN BOND

KW - TOPOLOGICAL ANALYSIS

KW - ELECTRON LOCALIZATION FUNCTION

UR - http://www.scopus.com/inward/record.url?scp=85094161274&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/d0e89353-cecc-37fd-8c9f-23eb91613fee/

U2 - 10.1002/chem.202002261

DO - 10.1002/chem.202002261

M3 - Article

AN - SCOPUS:85094161274

VL - 26

SP - 16338

EP - 16348

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 69

ER -