Reaction of Ni(NCS)(2) with 4-aminopyridine in different solvents leads to the formation of compounds with the compositions Ni(NCS)(2)(4-aminopyridine)(4) (1), Ni(NCS)(2)((4)-aminopyridine)(2)(H2O)(2) (2), [Ni(NCS)(2)(4-aminopyridine)(3)(MeCN)]center dot MeCN (3), and [Ni(NCS)(2)(4-aminopyridine)(2)](n) (5-LT). Compounds 1, 2, and 3 form discrete complexes, with octahedral metal coordination. In 5-LT the Ni cations are linked by single thiocyanate anions into chains, which are further connected into layers by half of the 4-aminopyridine coligands. Upon heating, 1 transforms into an isomer of 5-LT with a 1D structure (5-HT), that on further heating forms a more condensed chain compound [Ni(NCS)(2)(4-aminopyridine)](n) (6) that shows a very unusual chain topology. If 3 is heated, a further compound with the composition Ni(NCS)2(4-aminopyridine)3 (4) is formed, which presumably is a dimer and which on further heating transforms into 6 via 5-HT as intermediate. Further investigations reveal that 5-LT and 5-HT are related by enantiotropism, with 5-LT being the thermodynamic stable form at room-temperature. Magnetic and specific heat measurements reveal ferromagnetic exchange through thiocyanate bridges and magnetic ordering due to antiferromagnetic interchain interactions at 5.30(5) K and 8.2(2) K for 5-LT and 6, respectively. Consecutive metamagnetic transitions in the spin ladder compound 6 are due to dipolar interchain interactions. A convenient formula for susceptibility of the ferromagnetic Heisenberg chain of isotropic spins S = 1 is proposed, based on numerical DMRG calculations, and used to determine exchange constants.