The reaction Of Znl(2) and pyrimidine in acetonitrile results in the formation of the 1:2 compound Znl(2)(pyrimidine)(2) (1), which consists of discrete tetrahedral building blocks. Slow heating of 1 at 1 degrees C/min leads to its transformation into the ligand-deficient intermediate 1:1 compound Znl(2)(pyrimidine) (3), which upon further heating decomposes into the most ligand-deficient 2:1 compound (Znl(2))(2)(pyrimidine) (4). In contrast, the 2:3 compound (Znl(2))(2)(pyrimidine)(3) (2) is formed as an intermediate by decomposing 1 using a faster heating rate of 8 degrees C/min. Compound 2 consists of oligomeric units in which each Znl(2) unit is coordinated by two iodine atoms and one bridging and one terminal pyrimidine ligand. The crystal structure of compound 3 is built up of Znl(2) units, which are connected by the ligands into chains. For the thermal transformation of 1 into 3 via 2 as the intermediate, a smooth reaction pathway is found in the crystal structure, for which only small translational and rotational changes are needed. The metastable solvated compound (Znl(2))(pyrimidine)(acetonitrile)(0.25) (5) consisting of (Znl(2))(4)(pyrimidine)(4) rings is obtained by quenching the reaction of Znl(2) and pyrimidine in acetonitrile using an antisolvent. On heating, 5 decomposes into a new polymorphic 1:1 compound 6, which consists of (Znl2)(pyrimidine) chains. On further heating, 6 transforms into a third polymorphic 1:1 compound 7, which consists of (Znl(2))(3)(pyrimidine)(3) rings, and finally into the 1:1 compound 3. Solvent-mediated conversion experiments reveal that compounds 1-4 are thermodynamically stable, whereas compounds 5-7 are metastable. Time-dependent crystallization experiments unambiguously show that compound 7 is formed by kinetic control and transforms within minutes into compound 6, which finally transforms into 3. Compound 3 represents the thermodynamically most stable 1:1 modification, whereas compounds 6 and 7 are metastable. The different compounds obtained by thermal decomposition and by crystallization from solution represent a snapshot of the species in solution and thus provide insight into the formation of coordination compounds.