Playing with [{Mo₆Brⁱ₆Seⁱ₂}(CN)^a₆]⁴⁻ Cluster Building Blocks and Mn(salen)⁺ Nodes for the Crystal Engineering of Inorganic Coordination Polymers

Abstract

Dedicated to Antoine Maignan on the occasion of his 60 th birthday.We present here the syntheses and structural characterizations of inorganic polymeric cluster compounds, Cs[Mn-(salen)] 3 [{Mo 6 Br 6 Se 2 }(CN) 6 ](1) and (H 3 O)(TBA)[Mn-(salen)] 2 [{Mo 6 Br 6 Se 2 }(CN) 6 ] (2) (TBA = tetrabutylammonium ((n-C 4 H 9 ) 4 N + )), built-up from [{Mo 6 Br 6 Se 2 }(CN) 6 ] 4À molecular building blocks and Mn(salen) + complexes (salen = salen = N,N'bis(salicylidene)ethylenediamine). The nature of additional counter cations (i. e. Cs + or TBA + ) enables to control the interactions between the [{Mo 6 Br 6 Se 2 }(CN) 6 ] 4À building blocks and the Mn-(salen) + groups. Thus, 1 was obtained by slow diffusion of a methanol solution of K 2 Cs 2 [{Mo 6 Br 6 Se 2 }(CN) 6 ] cluster compound into a methanol solution of Mn(salen)ClO 4 . 2 was obtained in a similar way but after the addition of tetrabutylammonium bromide into the solution of Mn(salen)ClO 4 . 1 is a bimetallic 3D coordination compound (R � 3c) and 2 is a bimetallic 2D compound (P � 1). Structural correlations between 1 and 2 are discussed and compared with relevant examples found in the literature.