Reaction of (NPr 4 ) 3 [WS 4 Cu 3 I 4 ] 1, which is prepared by addition of CuI to (NPr 4 ) 2 [WS 4 ], with CuCl in dichloromethane gave crystals of (NPr 4 ) 3 [WS 4 Cu 5 I 6 ] 3 (orthorhombic, space groupPbnm (standard Pnma No 62),a = 13.130(6), b = 20.829(12), c = 22.715(5) a, Z = 4, R = 0.0504). The crystal structure revealed discrete [WS 4 Cu 5 I 6 ] - 3 anions separated by NPr 4 + cations; the anionic framework consists of a (WS 3 Cu 3 I) cube with two additional faces. Addition of NEt 4 Cl to (NPr 4 ) 3 [WS 4 Cu 3 Br 4 ] 2 in dichloromethane yielded red crystals of (NEt 4 ) 4 [WS 4 Cu 5 Br 7 ] 7 (monoclinic, space group C2c, a = 22.866(5), b = 10.760(2), c = 21.960(9) a, Z = 4,R = 0.0626). The two isostructural compounds (NEt 4 ) 3 [WS 4 Cu 5 Cl 7 ] 8 and (NEt 4 ) 3 [WS 4 Cu 5 Cl 1 . 5 I 5 . 5 ) 6 were characterized. The reactivity of these compounds was examined together with the relationships that exist with various copper thiometalate compounds characterized previously.