The reaction of W 6 Br 12 with AgBr in evacuated silica tubes (temperature gradient 925 K/915 K) yielded brownish black octahedra of Ag[W 6 Br 14 ] (I) and yellowish green platelets of Ag 2 [W 6 Br 14 ] (II) both in the low temperature zone. (I) crystallizes cubically (Pn3 (no. 201); a = 13.355 A Ê , Z = 4) and (II) monoclinically (P2 1 /c (no. 14); a = 9.384 A Ê , b = 15.383 A Ê , c = 9.522 A Ê , b = 117.34°, Z = 2). Both crystal structures contain isolated cluster anions, namely [(W 6 Br i 8 )Br a 6 ] 1± and [(W 6 Br i 8 )Br a 6 ])] 2± , respectively, with the mean distances and angles: (I) d(W±W) = 2.648 A Ê , d(W±Br i ) = 2.617 A Ê , d(W±Br a ) = 2.575 A Ê , d(Br i ´´´Br i ) = 3.700 A Ê , d(Br i ´´´Br a ) = 3.692 A Ê , ÐW±Br i ±W = 60.78°. (II) d(W±W) = 2.633 A Ê , d(W±Br i ) = 2.624 A Ê , d(W±Br a ) = 2.613 A Ê , d(Br i ´´´Br i ) = 3.710 A Ê , d(Br i ´´´Br a ) = 3.707 A Ê , ÐW±Br i ±W = 60.23°. The Ag + cations are trigonal antiprismatically coordinated in (I) with d(Ag±Br) = 2.855 A Ê , but distorted trigonally planar in (II) with d(Ag±Br) = 2.588± 2.672 A Ê . The structural details of hitherto known compounds with [W 6 Br 14 ] anions will be discussed.