Two novel CoII metal–organic frameworks {[Co(BIMB)2(H2O)2](SO4)·EG·3 H2O}n (I) and {[Co(TIMB)2](SiF6)}n (II) were hydrothermally synthesized by corresponding metal salt with organic ligands 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene (TIMB) or 1,4-bis((1H-imidazol-1-yl)methyl)benzene (BIMB). Crystal structural analysis reveals that they exhibit varied structures. Compound I contains two crystallographically unique CoII centers, each lying on an inversion center and having a slightly distorted octahedral environment. The BIMB ligands link the CoII cations to generate a three-dimensional porous framework with a 4-connected uninodal (65.8) topology. Compound II exhibits a two-dimensional sheeted metal-organic structure running parallel to the (0 0 1) plane, in which TIMB ligands join Co2+ centers having a six-coordinated octahedral structure. In the solid state, adjacent sheets are further bridged by guest SiF6- anions via C–H...F hydrogen-bonding interactions, giving rise to a three-dimensional supramolecular network structure with a 2-nodal (3-c)2(6-c) net. The topological analysis suggests that the point Schläfli symbol of compound II is (43)2(46.66.83). In addition, their thermal stabilities have also been investigated. [ABSTRACT FROM AUTHOR]