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)·7nH(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.