To seek the effect that condition of the complexes has on the manufacture of the biaryl compounds, seven Ni(II) complexes, namely, {[Ni(L)(0.5)(bpa)(H2O)]center dot 2H(2)O}(n), (1), {[Ni-2(L)(dpp)(2)(H2O)]center dot 4H(2)O}(n) (2), ([Ni(L)(0.5)(pbmb)(H2O)]center dot H2O}(n) (3), {[Ni-2(L)(bmp)(2)-(H2O)]center dot 7H(2)O}(n) (4), {[Ni(L)(0.5)(pbib)(1.5)]center dot 2H(2)O}(n) (5), {[Ni-2(L)-(pbib)(1.5)]center dot 3H(2)O}(n) (6), and [Ni(L)(0.5)(beb)(2)(H2O)], (7) (bpa = 1,2-bis(4-pyridyl)ethane, dpp = 1,3-di(4-pyridyl)propane, pbmb = 1,1'(1,3-propane)bis(2-methylbenzimidazole), bmp = 1,5-bis(2-methyl-benzimidazol) pentane, pbib = 1,4-bis(imidazol-1-ylmethyl)benzene, beb = 1,4-bis(2-ethylbenzimidazol-1-ylmethyl)benzene), have been gained through hydro(solvo)thermal reactions of 5,5'-(hexane-1,6-diyl)-bis(oxy)diisophthalic acid ligand (H4L) with Ni(II) metal ions under the regulation and control of six N-donor ligands. 3-fold interpenetrating complex 1 belongs to a (4,4)-connected 3D bbf net with a vertex symbol of (6(4)center dot 8(2))(6(6)) topology. 3-fold interpenetrating complex 2 presents a (4,4,4)-connected 3D bbf net with a Schldfli symbol of (6(6))(2)(6(4)center dot 8(2)) topology. 3 features a (3,4)-connected 3,4L13 topology with a Schldfli symbol of (4 center dot 6(2))(4(2)center dot 6(2)center dot 8(2)) topology. 4 possesses a (4,4,4)-connected mog Moganite 3D network fabric, and the vertex symbol is (4 center dot 6(4)center dot 8)(2)(4(2)center dot 6(2)center dot 8(2)). 5 takes on a (4,5)-connected architecture, and the point symbol is (4 center dot 6(9))(4(2)center dot 6(6)center dot 8(2)). 6 is a (4,7)-connected framework, and the Schlifli symbol is (4(5)center dot 5)(4(7)center dot 5(3)center dot 6(11)). 7 has a (4,4)-connected 4,4L28 topology, and the point (Schldfli) symbol is (4(2)center dot 6(4))(4 center dot 6(4)center dot 8). A systematic structural comparison of 1-7 signifies that their frameworks can be regulated through varied conformations of the flexible H4L ligand and diverse N-donor ligands. Between the proximal Ni(II) ions, the variable-temperature (2-300 K) magnetic susceptibilities of 6 display overall weak antiferromagnetic coupling. In the complexes-catalyzed homocoupling reaction of iodobenzene, 3, 5, 6, and 7 have been verified to be effectual catalysts for the synthesis of the biaryl compounds.