Monodentate and bridging behaviour of the sulfur-containing ligand 4'-[4-(methylsulfanyl)phenyl]-4,2':6',4''-terpyridine in two discrete zinc(II) complexes with acetylacetonate.

The Zn complexes bis(acetylacetonato-κ(2)O,O')bis{4'-[4-(methylsulfanyl)phenyl]-4,2':6',4''-terpyridine-κN(1)}zinc(II), [Zn(C(5)H(7)O(2))(2)(C(22)H(17)N(3)S)(2)], (I), and {μ-4'-[4-(methylsulfanyl)phenyl]-4,2':6',4''-terpyridine-κ(2)N(1):N(1'')}bis[bis(acetylacetonato-κ(2)O,O')zinc(II)], [Zn(2)(C(5)H(7)O(2))(4)(C(22)H(17)N(3)S)], (II), are discrete entities with different nuclearities. Compound (I) consists of two centrosymmetrically related monodentate 4'-[4-(methylsulfanyl)phenyl]-4,2':6',4''-terpyridine (L1) ligands binding to one Zn(II) atom sitting on an inversion centre and two centrosymmetrically related chelating acetylacetonate (acac) groups which bind via carbonyl O-atom donors, giving an N(2)O(4) octahedral environment for Zn(II). Compound (II), however, consists of a bis-monodentate L1 ligand bridging two Zn(II) atoms from two different Zn(acac)(2) fragments. Intra- and intermolecular interactions are weak, mainly of the C-H···π and π-π types, mediating similar layered structures. In contrast to related structures in the literature, sulfur-mediated nonbonding interactions in (II) do not seem to have any significant influence on the supramolecular structure.