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

Katherine A Bussey; Annie R Cavalier; Jennifer R Connell; Margaret E Mraz; Kayode D Oshin; Tomislav Pintauer; Allen G Oliver

doi:10.1107/S2053229615010335

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

Acta Crystallogr C Struct Chem. 2015 Jul;71(Pt 7):526-33. doi: 10.1107/S2053229615010335. Epub 2015 Jun 13.

Authors

Katherine A Bussey¹, Annie R Cavalier¹, Jennifer R Connell¹, Margaret E Mraz¹, Kayode D Oshin¹, Tomislav Pintauer², Allen G Oliver³

Affiliations

¹ Department of Chemistry & Physics, Saint Mary's College, Notre Dame, IN 46556, USA.
² Department of Chemistry & Biochemistry, Duquesne University, Pittsburgh, PA 15282, USA.
³ Department of Chemistry & Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA.

PMID: 26146388
DOI: 10.1107/S2053229615010335

Abstract

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-κ(3)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-κ(5)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-κ(3)N,N',N''}copper(II) dichloromethane monosolvate, [CuCl2(C15H17N3)]·CH2Cl2, (3), chlorido{(prop-2-en-1-yl)bis[(pyridin-2-yl)methylidene]amine-κ(3)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-κ(3)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.

Keywords: Atom Transfer Radical Addition (ATRA) reactions; coordination chemistry; copper scorpionates; crystal structure; hetero-scorpionates.