3D H-bonding networks self-assembly from pyridinium derivatives and bis(maleonitriledithiolato)zincate(II)

The two ion-pair complexes, [pyH](2)[Zn(mnt)(2)] (1) and [4,4'-bipyH(2)]-[Zn(mnt)(2)] (2), were synthesized, where mnt(2-) denotes maleonitriledithiolate, and [pyH](+), [4,4 -bipyH(2)](2+) represent pyridinium and diprotonated 4,4'-bipyridinium, respectively. Their single crystal structures show that there are strong bifurcated H-bonding interactions between the cations of the pyridinium derivative and the [Zn(mnt)2]2 - anions in both 1 and 2. The bifurcated H-bonding interactions between the N-H of the pyridiniums and the CN groups of the mnt(2-) ligands give rise to a 2D layered H-bonding network, the adjacent layers come together in such way as mutual embrace to give a tight pack, thus 2D hydrogen-bonding sheets further develop into 3D H-bonding networks through weak C-(HS)-S-... and pi(...)pi stacking interactions in 1. As for 2, the cations and anions connect into several types of H-bonding macrorings ([2 + 2], [3 + 3] and [4 + 41), these H-bonding macrorings fuse to extend into 2D layered structure, the interpenetration between [3 + 3] and [4 + 4] type H-bonding macrorings in the adjacent layers give further rise to novel 3D extended H-bonding networks, in which there are clearly parallel stacks of cations and the chelate rings of anions. (C) 2003 Elsevier B.V. All rights reserved.