Hydrogen-bonding interactions between linear bipyridinium cations and nitrate anions

Abstract

A series of diprotonated bipyridium nitrates has been synthesised. The bipyridines considered are 4,4-bipyridine (bipy), trans-1,2-bis(pyridin-4-yl)ethene (bpe), 4,4-azobis(pyridine) (diazobpe), 3,6-bis(pyridin-4-yl)-1,2,4,5-tetrazine (pytz), 3,6-bis(imidazol-1-yl)pyridazine (ipd) and 1,4-bis[(4,4-pyridyl)ethenyl]benzene (bpeb). A total of seven structures are discussed: two polymorphs of each of H2bipy(NO3)2 and H2bpe(NO3)2 and one crystal form of each of H2diazobpe(NO3)2, H2bpeb(NO3)2 and H2ipd(NO3)2. Both N–H⋯O and C–H⋯O hydrogen-bonds are thought to be structure determining. The structural parameters of the N–H⋯O contacts fall into extremely narrow ranges: in contrast, the structural parameters for the C–H⋯O contacts differ widely and are considered to fall into three distinct types. Evidence for the importance of C–H⋯O hydrogen-bonds arises primarily from the different structures of the salts formed by [H2bpe]2+ and [H2diazobpe]2+ which differ solely in the ethene/diazo moiety linking the pyridine rings. The C–H donors of the ethene-link of the [H2bpe]2+ cation form hydrogen-bonds to the nitrate anion thereby generating a 2-D sheet structure. In the absence of these donors, the anions act as μ-O,O' bridging units linking neighbouring diazo-linked [H2diazobpe]2+ cations in adjacent unit cells. Secondary support for the significance of C–H⋯O interactions comes from the recurrence of particular hydrogen-bonding ring and chain motifs. Evidence for the delicate energy balance between different structures comes from the formation of the two pairs of polymorphs.