Facile Transformation of Isolated Fragments to Infinite Chains in Rhenium Chalcocyanide Clusters: Synthesis and Structure of (Pr4N)2M(H2O)5 [Re6X8(CN)6]·H2O and (Pr4N)2M(H2O)4[Re6S8(CN)6] (X=S, Se; M=Mn, Ni)

✍ Scribed by N.G. Naumov; S.B. Artemkina; A.V. Virovets; V.E. Fedorov

• Publisher: Elsevier Science
• Year: 2000
• Tongue: English
• Weight: 260 KB
• Volume: 153
• Category: Article
• ISSN: 0022-4596
• DOI: 10.1006/jssc.2000.8736

✦ Synopsis

R1 ‫؍‬ 0.0387, wR2 ‫؍‬ 0.0624), (Pr 4 N) 2 Mn(H 2 O) 4 [Re 6 S 8 (CN) 6 ] (space group: I4/m, a ‫؍‬ 13.255(2) A s , c ‫؍‬ 14.432(3) A s , V ‫؍‬ 2535.6(8) A s 3 , R1 ‫؍‬ 0.0369, wR2 ‫؍‬ 0.0960) and (Pr 4 N) 2 Ni (H 2 O) 4 [Re 6 S 8 (CN) 6 ] (space group: I4/m, a ‫؍‬ 13.247(4) A s , c ‫؍‬ 14.246(6) A s , V ‫؍‬ 2500(2) A s 3 , R1 ‫؍‬ 0.0414, wR2 ‫؍‬ 0.1004) were determined by X-ray single crystal analysis. The structure of (Pr 4 N) 2 Mn(H 2 O) 5 [Re 6 Se 8 (CN) 6 ] ' H 2 O contains isolated fragments +Mn(H 2 O) 5 [Re 6 Se 8 (CN) 6 ], 2؊ . The structures of (Pr 4 N) 2 M(H 2 O) 4 [Re 6 S 8 (CN) 6 ] (M ‫؍‬ Mn, Ni) contain +-Mn(H 2 O) 4 -[Re 6 S 8 (CN) 6 ]-, 2؊ in5nite chains. When heated the (Pr 4 N) 2 M(H 2 O) 5 [Re 6 S 8 (CN) 6 ] ' H 2 O compounds transform into (Pr 4 N) 2 M(H 2 O) 4 [Re 6 S 8 (CN) 6 ], the reaction conditions depending on the nature of the metal. The formation and conversion of the compounds are discussed in terms of substitution of water molecules in coordination sphere of transition metal cations. It is shown that the orthorhombic structure can be considered as a superstructure in respect to the tetragonal one.