A Tail Does Not Always Make a Difference: Assembly of cds Nets from Co(NCS)(2) and 1,4-bis(n-Alkyloxy)-2,5-bis(3,2′:6′,3″-terpyridin-4′-yl)benzene Ligands

The consistent assembly of a (6(5).8) cds net is observed in reactions of cobalt(II) thiocyanate with 1,4-bis(n-alkyloxy)-2,5-bis(3,2′:6′,3″-terpyridin-4′-yl)benzene ligands in which the n-alkyloxy substituents are n-propyl (ligand 3), n-butyl (4), n-pentyl (5), n-hexyl (6), n-heptyl (7), and n-octyl (8). Crystals were grown by layering a methanol solution of Co(NCS)(2) over a 1,2-dichlorobenzene solution of each ligand. The choice of crystallization solvents is critical in directing the assembly of the cds net. Single-crystal structures of [Co(NCS)(2)(3)](n)(.)3.5nC(6)H(4)Cl(2), [Co(NCS)(2)(4)](n)(.)5.5nC(6)H(4)Cl(2), [Co(NCS)(2)(5)](n)(.)4nC(6)H(4)Cl(2), [Co(NCS)(2)(6)](n)(.)3.8nC(6)H(4)Cl(2), [Co(NCS)(2)(7)](n)(.)3.1nC(6)H(4)Cl(2), and [Co(NCS)(2)(8)](n)(.)1.6nC(6)H(4)Cl(2)(.)2nMeOH (C(6)H(4)Cl(2) = 1,2-dichlorobenzene) are presented and compared. The n-alkyloxy chains exhibit close to extended conformations and are accommodated in cavities in the lattice without perturbation of the coordination framework.