An unusual two-dimensional hydrogen-bonding network in bis(2,9-dimethyl-1,10-phenanthrolin-1-ium) peroxodisulfate dihydrates

Abstract

The title compound, 2C(14)H(13)N(2)(+)center dot S2O82-center dot 2H(2)O, is a protonated amine salt which is formed from two rather uncommon ionic species, namely a peroxodisulfate (pds(2-)) anion, which lies across a crystallographic inversion centre, and a 2,9-dimethyl1,10-phenanthrolin-1-ium (Hdmph(+)) cation lying in a general position. Each pds(2-) anion binds to two water molecules through strong water-peroxo O-H center dot center dot center dot O interactions, giving rise to an unprecedented planar network of hydrogen-bonded macrocycles which run parallel to (100). The atoms of the large R-8(8)(30) rings are provided by four water molecules bridging in fully extended form (center dot center dot center dot H-O-H center dot center dot center dot) and four pds(2-) anions alternately acting as long (center dot center dot center dot O-S-O-O-S-O center dot center dot center dot) and short (center dot center dot center dot O-S-O center dot center dot center dot) bridges. The Hdmph(+) cations, in turn, bind to these units through hydrogen bonds involving their protonated N atoms. In addition, the crystal structure also contains pi-pi and aromatic-peroxo C-H center dot center dot center dot O interactions.