Reactions of [Et 4N] 2[MoS 4(CuCN) 2]·H 2O with bis-(4-pyridyl)propane (bpp) and [Cu(MeCN) 4][ClO 4] in aniline produced [MoS 4Cu 4(bpp) 2(CN) 2] ·; 1.5(aniline) (1a). 1a consists of a new three-dimensional [MoS 4Cu 4]-supported open coordination polymer which has a relatively large channel with a volume of ca. 618 A 3 per unit cell. 1a underwent a two-step host-guest process in which the aniline molecules residing in its channels could be partly exchanged with MeCN molecules in 3d and then completely with dimethylformamide molecules in a month, forming {[MoS 4Cu 4(bpp) 2(CN) 2]· (aniline)-(MeCN)} n (1b) and {[MoS 4Cu 4(bpp) 2(CN) 2]·(DMF)·(MeCN)} n (1c), respectively. © 2008 American Chemical Society.