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 . 3.5 n C 6 H 4 Cl 2 , [Co(NCS) 2 ( 4 )] n . 5.5 n C 6 H 4 Cl 2 , [Co(NCS) 2 ( 5 )] n . 4 n C 6 H 4 Cl 2 , [Co(NCS) 2 ( 6 )] n . 3.8 n C 6 H 4 Cl 2 , [Co(NCS) 2 ( 7 )] n . 3.1 n C 6 H 4 Cl 2 , and [Co(NCS) 2 ( 8 )] n . 1.6 n C 6 H 4 Cl 2 . 2 n MeOH (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.