Abstract
One pentacoordinated mononuclear complex [Zn(L)(NCS)]PF6 (1), one hexacoordinated 2D coordination polymer {[Cd2(L)(NCS)4]·0.24(CH3OH)}n (2) and one pentacoordinated 1D polymeric chain [Hg2(L)(SCN)4]n (3) [L=N,N′-(bis(pyridine-2-yl)benzylidene)-1,4-butanediamine] have been synthesized and X-ray crystallographically characterized. Structural analyses revealed interesting variations in the coordination behaviour of the Schiff base (L) from tetradentate chelation to binucleating bis(bidentate) congregation on going from 1 to 2/3. The pseudohalide exhibits terminal N-coordination in 1, both μ1,3 and μ1,1 bridges in 2 and terminal S-coordination along with μ1,1 linkages in 3. In 1/3, each pentacoordinated zinc(II)/mercury(II) centre adopts a distorted trigonal bipyramidal/square pyramidal geometry with a ZnN5/HgN2S3 chromophore, whereas both Cd1 and Cd2 centres in 2 adopt a distorted octahedral geometry with CdN3S3 and CdN6 chromophores, respectively. Weak intermolecular S···S and S···π interactions with multiple C–H···N hydrogen bonds promote the dimensionalities in 1–3. The complexes display intraligand 1(π–π∗) fluorescence in the solid state and in DMF solutions at room temperature.
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