A three-dimensional coordination polymer,[Ni（Hbyip2-）（bix）0.5（H2O）]n,has been hydrothermally synthesized.Each Ni2＋ ion is five-coordinated by three carboxylate O atoms from three different 5-（benzoic acid-4-yldiazenyl）isophthalate（Hbyip2-） anions,one N atom from one 1,4-bis（imidazol-1-ylmethyl）benzene（bix） ligand and one O atom from an aqua ligand displaying a distorted square-pyramid.Each Ni atom is defined by three Hbyip2-anions and each Hbyip2-anion adopts a tris（mono-dentate） ligand coordinating to three Ni2＋ ions affording a 36-membered inorganic ring.These rings are further arranged into an undulated two-dimensional layer parallel to the（101） plane.Adjacent two-dimensional networks are linked by bix ligands into a three-dimensional {63,83}{63} framework with a large channel（ca.26.3 × 13.6） along the [100] direction.Each individual {63,83}{63} network interpenetrates with two others in a parallel fashion to generate a 3-fold interpenetrating network.
The title coordination polymer including two crystallographically independent Co2＋ ions is hydrothermally synthesized, in which the Co（1） 2＋ ion is four-coordinated by two carboxylate oxygen atoms from two different 5-（benzoic acid-4-yldiazenyl）isophthalate （byip3-） anions and two nitrogen atoms from two distinct 1,4-bis（imidazol-1-ylmethyl） benzene （bix） ligands displaying a tetrahedral geometry. The Co（2） 2＋ ion is six-coordinated by two water molecules at the apical positions, and two carboxylate oxygen atoms and two nitrogen atoms at the equatorial positions, affording a slightly distorted octahedron. Two Co（1）2＋ and two Co（2）2＋ ions are linked together by four byip3- anions forming a 44-membered motif and these motifs are further arranged into a three-dimensional framework through bix ligands along the a axis with a larger channel （ca. 22.70×11.01）. Each individual network interpenetrates with the other identical network in a parallel fashion to generate a 2-fold interpenetrating array with the {62.84}{63}2{64.82}2 topology.
