Statistical analysis of noncovalent interactions of anion groups in crystal structures. I. Hydrogen bonding of sulfate anions

Abstract

The hydrogen-bond acceptor characteristics of sulfate dianions are analyzed in crystal structures of small molecules. For 85 anions, neither coordinated to metal ions nor covalently bonded, 697 hydrogen bonds are faund. Of these, 266 (38%) are the O...H—O type and 431 (62%) are the O...H—N type, proportions that correspond well to the stoichiometry of the compounds studied and indicate no preference for a particular donor. The analysis of the data set, after classifying the hydrogen bonds according to the different types of donors, shows that O...H—O bonds are more linear than O...H—N. The anion oxygen–acceptor function is characterized by multiple hydrogen bonding. Only in 56 cases does a sulfate oxygen participate in a single hydrogen bond. In most cases every sulfate oxygen is coordinated by two (187 cases) or three (89 cases) hydrogen bonds. For three H donors, the preferred coordination geometry of the sulfate oxygen is pyramidal. The most frequent coordination around a sulfate dianion is with eight to ten H donors. Thus, sulfate dianions can play a significant cohesive role in molecular aggregation.