Three new metal coordination polymers of bifunctional imidazolate/tetrazolate bridges: the only example of a three-dimensional framework based on rare [Co 4 (μ 3 -OH) 2 (μ 2 -Cl) 2 ] 4+ mixed oxo-chloro-clusters.

Three new metal coordination polymers [Ni(μ 2 -L) 2 (H 2 O) 2 ] n (1, HL = 1-tetrazole-4-imidazole-benzene), [Co(μ 2 -L) 2 ] n (2), and [Co 4 (μ 3 -OH) 2 (μ 2 -Cl) 2 (μ 5 -L) 2 (μ 2 -L) 2 ] n ·7 n H 2 O (3) were hydrothermally synthesized and structurally characterized. 1 displays a neutral [Ni(μ 2 -L) 2 (H 2 O) 2 ] n chain built up from the Ni 2+ ions bridged by deprotonated L - ligands, while 2 shows another rare neutral [Co(μ 2 -L) 2 ] n chain based on Co 2+ ions connected by two different coordination modes of the L - ligand. 3 exhibits a rare [Co 4 (μ 3 -OH) 2 (μ 2 -Cl) 2 ] 4+ mixed oxo-chloro-cluster-based three-dimensional framework with large elliptical channels, which are filled by unprecedented chilopod [(H 2 O) 7 ] n chains. Both 1 and 2 show antiferromagnetic behavior, while 3 exhibits unusual spin-canting.