Doubly bridged heptacoordinated cadmium(II) compounds containing a tetradentate Schiff base: Variance in molecular and crystalline architectures with pseudohalides

Two heptacoordinated dinuclear complexes of the type [Cd(bpbe)(X)₂]₂ · nH₂O [bpbe = N,N'-(bis(pyridin-2-yl)benzylidene)ethane-1,2-diamine; X = N₃^-, n = 2, 1; X = NCS^-, n = 0; 2] are prepared and the structures are solved by X-ray study that reveals interesting variation in bridging motifs of the pseudohalides from bibridged end-on (in 1) to bibridged end-to-end (in 2). The hydrated dinuclear units in 1 pack through O-H...N, C-H...O, and C-H...N hydrogen bonds along with p...p interaction leading to an infinite 1D chain and the dinuclear units in 2 are engaged in p...p interactions resulting a 2D sheet structure. They display intraligand ¹(p-p^*) fluorescence and ³(p-p^*) phosphorescence in glassy solutions. © 2006 Elsevier B.V. All rights reserved.