A trinuclear palladium(II) complex containing N,S-coordinating 2-(benzylsulfanyl)anilinide and 1,3-benzothiazole-2-thiolate ligands with a central square-planar PdN4 motif

Edward D Cross; Kristen L MacDonald; Robert McDonald; Matthias Bierenstiel

doi:10.1107/S2053229613032828

A trinuclear palladium(II) complex containing N,S-coordinating 2-(benzylsulfanyl)anilinide and 1,3-benzothiazole-2-thiolate ligands with a central square-planar PdN4 motif

Acta Crystallogr C Struct Chem. 2014 Jan;70(Pt 1):23-7. doi: 10.1107/S2053229613032828. Epub 2013 Dec 14.

Authors

Edward D Cross¹, Kristen L MacDonald¹, Robert McDonald², Matthias Bierenstiel¹

Affiliations

¹ Department of Chemistry, Cape Breton University, 1250 Grand Lake Road, Sydney, Nova Scotia, Canada B1P 6L2.
² X-ray Crystallography Laboratory, Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2.

PMID: 24399220
DOI: 10.1107/S2053229613032828

Abstract

The reaction of dichlorido(cod)palladium(II) (cod = 1,5-cyclooctadiene) with 2-(benzylsulfanyl)aniline followed by heating in N,N-dimethylformamide (DMF) produces the linear trinuclear Pd3 complex bis(μ2-1,3-benzothiazole-2-thiolato)bis[μ2-2-(benzylsulfanyl)anilinido]dichloridotripalladium(II) N,N-dimethylformamide disolvate, [Pd3(C7H4NS2)2(C13H12NS)2Cl2]·2C3H7NO. The molecule has -1 symmetry and a Pd...Pd separation of 3.2012 (4) Å. The outer Pd(II) atoms have a square-planar geometry formed by an N,S-chelating 2-(benzylsulfanyl)anilinide ligand, a chloride ligand and the thiolate S atom of a bridging 1,3-benzothiazole-2-thiolate ligand, while the central Pd(II) core shows an all N-coordinated square-planar geometry. The geometry is perfectly planar within the PdN4 core and the N-Pd-N bond angles differ significantly [84.72 (15)° for the N atoms of ligands coordinated to the same outer Pd atom and 95.28 (15)° for the N atoms of ligands coordinated to different outer Pd atoms]. This trinuclear Pd3 complex is the first example of one in which 1,3-benzothiazole-2-thiolate ligands are only N-coordinated to one Pd centre. The 1,3-benzothiazole-2-thiolate ligands were formed in situ from 2-(benzylsulfanyl)aniline.

Keywords: 1,3-benzothiazole-2-thiolate; 2-(benzylsulfanyl)anilinide; S-benzyl ortho-aminothiophenol; crystal structure; square-planar PdN4 motif; trinuclear palladium(II) complex.