The syntheses and characterizations of three new ligands containing two 4,2′:6′,4″-tpy or two 3,2′:6′,3″-tpy metal-binding domains are reported. The ligands possess different alkyloxy functionalities attached to the central phenylene spacer: n-pentyloxy in >3, 4-phenyl-n-butoxy in >4, benzyloxy in >5. Crystal growth under ambient conditions has led to the formation of {[Co(NCS)2(>3)]·0.8C6H4Cl2}n and {[Co(NCS)2(>4)]·1.6H2O·1.2C6H4Cl2}n, with structures confirmed by single crystal X-ray diffraction. Both the cobalt(II) center and ligand >3 or >4 act as 4-connecting nodes and both {[Co(NCS)2(>3)]·0.8C6H4Cl2}n and {[Co(NCS)2(>4)]·1.6H2O·1.2C6H4Cl2}n possess a 3D cds net despite the fact that >3 and >4 contain two 4,2′:6′,4″-tpy and two 3,2′:6′,3″-tpy units, respectively. Taken in conjunction with previously reported data, the results indicate that the role of the alkyloxy substituent is more significant than the choice of 4,2′:6′,4″- or 3,2′:6′,3″-tpy isomer in determining the assembly of a particular 3D net. The combination of Co(NCS)2 with >5 resulted in the formation of the discrete molecular complex [Co(NCS)2(MeOH)2(>5)2]·2CHCl3·2MeOH in which >5 acts as a monodentate ligand. The pendant phenyls and both coordinated and non-coordinated 4,2′:6′,4″-tpy units are involved in efficient π-stacking interactions.
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