Novel hydrogen bond network topologies in complexes of the ditopic ligand 5-amino-3-(pyrid-2-yl)-1H-pyrazole

The syntheses and crystal structures of [MnCl2L2]·2CH3OH (1·2CH3OH), [FeCl2L2]Cl·4CH3OH (2·4CH3OH), [Cu(ClO4)L2]ClO4·CH3OH (3·CH3OH), [Cu(NCMe)L2][ClO4]2 (4), [Cu(NO3)L2]NO3·xH2O (5·xH2O), [Zn(NO3)L2]NO3·xH2O (6·xH2O) and [Cu(μ-{L–H})(L–H)]2·xH2O (7·xH2O) are presented, where L = 5{3}-amino-3{5}-(pyrid-2-yl)-1H-pyrazole. In each case the ligand ‘L’ chelates to the metal cation through its pyridinyl and pyrazolyl N-donors, while the aminopyrazole moiety hydrogen bonds to coordinated or non-coordinated anions or solvent in the structure. This bifunctionality leads to extended hydrogen-bond networks. Of particular interest are 2·4CH3OH, whose six, four-connected network can be understood as a heavily modified derivative of the boron nitride topology; 3·CH3OH, which forms a network of linked ladders containing alternating five- and three-connected nodes; and, isostructural 5·xH2O and 6·xH2O, which form an extremely complicated network of four distinct nodes with connectivities of up to nine, depending on the presence or absence of a partially occupied water molecule.