[Ni 2 (dien) 2 (NCS) 4 (H 2 O)] (1) and [Ni(aepn)(NCS) 2 ] n (2) (where dien = bis(2-aminoethyl)amine and aepn = N-(2-aminoethyl)-1,3-propanediamine) have been synthesised from solution. Single crystal X-ray structure analyses of 1 and 2 reveal that the metal atoms in both the complexes display distorted octahedral geometry with the triamine coordinating facially in 1 and meridionally in 2. The dinuclear [Ni 2 (dien) 2 (NCS) 4 (H 2 O)] unit in 1 is bridged via a thiocyanate moiety while in 2 the nickel(II) octahedra form a polymeric chain. The species 1 on deaquation at 165°C followed by cooling yields a conglomerated mass (1a). The species 2 melts at 230°C which on cooling yields conglomerated mass (2a). Both 1a and 2a are amorphous; the former reverts to 1 in a humid atmosphere.