Reactions of transition-metal cations with [Re6Te 8(CN)6]4- (see abstract)
The compounds [Zn(NH 3 ) 4 ] 2 [Re 6 Te 8 (CN) 6 ] (1) , [{Co(NH 3 ) 5 } 2 Re 6 Te 8 (CN) 6 ] · 4H 2 O (2) , and [{Ni(NH 3 ) 5 } 2 Re 6 Te 8 (CN) 6 ] · 4H 2 O (3) have been synthesized by the diffusion of an ammonia solution of Cs 4 [Re 6 Te 8 (CN) 6 ] · 2H 2 O into a glycerol solution of ZnCl 2 (for 1 ), CoCl 2  · 6H 2 O (for 2 ), or NiCl 2  · 6H 2 O (for 3 ). Compound 1 crystallizes in the trigonal space group with one formula in a unit cell of dimensions a =10.3776(8) A, c =10.4322(11) A, and V =972.97(15) A 3 ( T =153 K). Compounds 2 and 3 crystallize with four formula units in space group C 2/ c with cells of dimensions a =20.808(2) A, b =22.027(3) A, c =10.3708(11) A, β =110.958(2)°, and V =4438.9(8) A 3 ( T =153 K) (for 2 ); a =20.7617(15) A, b =22.0521(16) A, c =10.3526(8) A, β =110.692(1)°, and V =4434.1(6) A 3 ( T =153 K) (for 3 ). Compound 1 is ionic whereas compounds 2 and 3 , which are isostructural, are molecular comprising two M(NH 3 ) 5 groups (M=Co, Ni) bonded in a trans fashion to the Re 6 Te 8 (CN) 6 cluster through M–N(cyanide) bonds.