3-D Coordination Network Structures Constructed from [W₆S₈(CN)₆]^6- Anions

Abstract

Octahedral molybdenum and tungsten clusters face-capped by chalcogens M6Q8 (M = Mo, W; Q = S, Se, Te) have drawn extensive attention because of the well-known molybdenum-based Chevrel phases. Water-soluble cyanide complexes of these clusters can be prepared by cluster excision from the solid-state compound Mo6Se8 or by ligand exchange from W6S8(4-tert-butylpyridine)6. The [W6S8(CN)6]6- cluster anion can, in turn, be used as a building block to construct 3-D extended coordination networks with transition metal cations M2+ (M = Mn, Fe, Co, Zn) as linking units. The novel 3-D structures were determined by X-ray crystallography to be two-fold interpenetrating distorted cubic networks of [M(II)(H2O)4]3[W6S8(CN)6]·xH2O (x ≈ 23; M = Mn, Fe, Co) or a rutile-like network of K2[Zn(H2O)2]2[W6S8(CN)6]·26H2O, both bridged through W−CN−M−NC−W linkages. The properties of the new network structures are investigated and factors relevant to the construction of network structures containing W6S8 clusters are discussed