Molecular Networks Created by Charge-Assisted Hydrogen
Bonding in Phosphonate, Phosphate, and Sulfonate Salts of Bis(amidines)
- Publication date
- Publisher
Abstract
Two
bis(amidines), 2,2′-bi-2-imidazoline (BI) and fluoflavin
(FF), were treated with phosphonic, phosphoric, and sulfonic acids
in an effort to produce crystalline salts composed of ions linked
by networks of charge-assisted hydrogen bonds. As intended, mixing
bis(amidine) BI with 1,4-benzenediphosphonic acid and 1,3,5-benzenetriphosphonic
acid yielded crystals of phosphonate salts of dication H<sub>2</sub>BI<sup>+2</sup>. Structural analyses showed that such salts tend
to incorporate tapes composed of alternating dications and anions
linked by multiple charge-assisted N–H···O hydrogen
bonds of type R<sub>2</sub><sup>2</sup>(9) and R<sub>2</sub><sup>1</sup>(7). Typically, the ionic tapes are further connected to form sheets
or other assemblies by additional O–H···O hydrogen
bonds involving phosphonate anions. An analogous reaction of the more
weakly basic bis(amidine) FF with 1,4-benzenedisulfonic acid yielded
only a sulfonate salt of monocation HFF<sup>+</sup>; however, diprotonation
could be achieved by phosphoric acid to produce a crystalline salt
built from stacks of H<sub>2</sub>FF<sup>+2</sup> dications linked
to phosphate anions by charge-assisted N–H···O
hydrogen bonds of type R<sub>2</sub><sup>2</sup>(8). Together, these results demonstrate that acids with multiple
PO(OH)<sub>2</sub> and SO<sub>2</sub>OH groups can react with bis(amidines)
to produce salts with structural features resulting predictably from
the geometry of the ions and their ability to engage in multiple charge-assisted
hydrogen bonds according to standard patterns