Structural studies of (prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine hetero-scorpionate copper complexes

The structures of five compounds consisting of (prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine complexed with copper in both the Cu^I and Cu^II oxidation states are presented, namely chlorido{(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ³ N,N′,N′′}copper(I) 0.18-hydrate, [CuCl(C15H17N3)].0.18H2O, (1), catena-poly[[copper(I)-μ2-(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ⁵ N,N′,N′′:C ²,C ³] perchlorate acetonitrile monosolvate], {[Cu(C₁₅H₁₇N₃)]ClO₄.CH₃CN} _n , (2), dichlorido{(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ³ N,N′,N′′}copper(II) dichloromethane monosolvate, [CuCl₂(C₁₅H₁₇N₃)].CH₂Cl₂, (3), chlorido{(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ³ N,N′,N′′}copper(II) perchlorate, [CuCl(C₁₅H₁₇N₃)]ClO₄, (4), and di-μ-chlorido-bis({(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ³ N,N′,N′′}copper(II)) bis(tetraphenylborate), [Cu₂Cl₂(C₁₅H₁₇N₃)₂][(C₆H₅)₄B]₂, (5). Systematic variation of the anion from a coordinating chloride to a noncoordinating perchlorate for two Cu^I complexes results in either a discrete molecular species, as in (1), or a one-dimensional chain structure, as in (2). In complex (1), there are two crystallographically independent molecules in the asymmetric unit. Complex (2) consists of the Cu^I atom coordinated by the amine and pyridyl N atoms of one ligand and by the vinyl moiety of another unit related by the crystallographic screw axis, yielding a one-dimensional chain parallel to the crystallographic b axis. Three complexes with Cu^II show that varying the anion composition from two chlorides, to a chloride and a perchlorate to a chloride and a tetraphenylborate results in discrete molecular species, as in (3) and (4), or a bridged bis-μ-chlorido complex, as in (5). Complex (3) shows two strongly bound Cl atoms, while complex (4) has one strongly bound Cl atom and a weaker coordination by one perchlorate O atom. The large noncoordinating tetraphenylborate anion in complex (5) results in the core-bridged Cu₂Cl₂ moiety.