Geometry of trigonal boron coordination sphere in boronic acids derivatives – a bond-valence vector model approach

Karolina Czerwińska , Izabela Madura , Janusz Zachara

Abstract

The systematic analysis of the geometry of three-coordinate boron in boronic acid derivatives with a common [CBO2] skeleton is presented. The study is based on the bond-valence vector (BVV) model [Zachara (2007). Inorg. Chem. 46, 9760-9767], a simple tool for the identification and quantitative estimation of both steric and electronic factors causing deformations of the coordination sphere. The empirical bond-valence (BV) parameters in the exponential equation [Brown & Altermatt (1985). Acta Cryst. B41, 244-247] rij and b, for B-O and B-C bonds were determined using data deposited in the Cambridge Structural Database. The values obtained amount to rBO = 1.364 Å, bBO = 0.37 Å, rBC = 1.569 Å, bBC = 0.28 Å, and they were further used in the calculation of BVV lengths. The values of the resultant BVV were less than 0.10 v.u. for 95% of the set comprising 897 [CBO2] fragments. Analysis of the distribution of BVV components allowed for the description of subtle in- and out-of plane deviations from the `ideal' (sp2) geometry of boron coordination sphere. The distortions specific for distinct groups of compounds such as boronic acids, cyclic and acyclic esters, benzoxaboroles and hemiesters were revealed. In cyclic esters the direction of strains was found to be controlled by the ring size effect. It was shown that the syn or anti location of substituents on O atoms is decisive for the deformations direction for both acids and acyclic esters. The greatest strains were observed in the case of benzoxaboroles which showed the highest deviation from the zero value of the resultant BVV. The out-of-plane distortions, described by the vz component of the resultant BVV, were ascertained to be useful in the identification of weak secondary interactions on the fourth coordination site of the boron centre.
Author Karolina Czerwińska KChNTCS
Karolina Czerwińska,,
- Chair Of Inorganic Chemistry And Solid State Technology
, Izabela Madura KChNTCS
Izabela Madura,,
- Chair Of Inorganic Chemistry And Solid State Technology
, Janusz Zachara KChNTCS
Janusz Zachara,,
- Chair Of Inorganic Chemistry And Solid State Technology
Journal seriesActa Crystallographica Section B-Structural Science, ISSN 0108-7681
Issue year2016
NoB72
Pages241-248
Publication size in sheets0.5
Keywords in Englishbond-valence vector model; coordination sphere deformations; boronic acid derivatives
DOIDOI:10.1107/S2052520616002262
URL http://scripts.iucr.org/cgi-bin/paper?S2052520616002262
Languageen angielski
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Score (nominal)30
ScoreMinisterial score = 30.0, 28-11-2017, ArticleFromJournal
Ministerial score (2013-2016) = 30.0, 28-11-2017, ArticleFromJournal
Publication indicators WoS Impact Factor: 2014 = 2.184 (2) - 2014=2.208 (5)
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