The compounds [Ni(en)(3)](2)[Re(6)Te(8)(CN)(6)].10H(2)O (1), [Ni(NH(3))(4)(en)](2)[Re(6)Te(8)(CN)(6)].2H(2)O (2), [Ni(NH(3))(2)(en)(2)][(Ni(en)(2))(3)(Re(4)Te(4)(CN)(12))(2)].38H(2)O (3), [Co(NH(3))(2)(en)(2)](2)[(Co(en)(2))Re(6)Te(8)(CN)(6)]Cl(2).H(2)O (4),and [(Zn(H(2)O)(en)(2))(Zn(en)(2))Re(6)Te(8)(CN)(6)].3H(2)O (5) (en = ethylenediamine) have been synthesized and characterized. Compounds 1, 4, and 5 have been synthesized by the diffusion of an aqueous (for 1 and 5) or an ammonia (for 4) solution of Cs(4)[Re(6)Te(8)(CN)(6)].2H(2)O into a glycerol solution of NiCl(2).6H(2)O (for 1), CoCl(2).6H(2)O (for 4), or ZnCl(2) (for 5). Compounds 2 and 3 have been synthesized by the reaction of an aqueous solution of Cs(4)[Re(6)Te(8)(CN)(6)].2H(2)O (for 2) or K(4)[Re(4)Te(4)(CN)(12)].5H(2)O (for 3) with an ammonia solution of Ni(en)(2)Cl(2). Compounds 1 and 2 are ionic whereas compounds 4 and 5 are one-dimensional polymers. Compound 3, a two-dimensional polymer, possesses hexagonal shaped channels of approximate diameter 10-12 A. Because the framework of compound 3 is robust, it is an attractive host for guest molecules of appropriate size and shape. The potential "guest" volume is about 37% of the unit cell volume.