Synthesis and crystal structures of coordination polymers, networks and complexes of an adamantane shaped phosphorus-nitrogen cage ligand and cuprous chloride

Reactions of cuprous chloride with the phosphorus-nitrogen cage ligand 2,4,6,8,9,10-hexamethyl-2,4,6,8,9,10-hexaaza-1,3,5,7-tetraphosphaadamantane, P-4(NCH3)(6), in acetonitrile form distinct solids depending on the ligand-to-metal ratio. Three structurally characterized compounds include: a solvated 3-D network of formula [P-4(NCH3)(6)](2)(CuCl)(3)(CH3CN)(2); a "ladder-type" Polymer {[mu(2)-P-4(NCH3)(6)](2) (CuCl)(2))}; and a monomeric complex [P-4(NCH3)(6)](2)CuCl. Thermal decomposition of the solvated network results in formation of two more materials [P-4(NCH3)(6)](2)(CuCl)(3), and [P-4(NCH3)(6)](CuCl)(2) that are not isolated from solution reactions. The variety of products isolated based solely on ligand-to-metal ratio suggest that this system participates in solution equilibria common to many phosphorus(III) ligands and multiple solubility equilibria. (C) 2010 Elsevier Ltd. All rights reserved.