[ N, N-Bis(2-hy-droxy-eth-yl)di-thio-carbamato-κ2S, S']bis-(tri-phenyl-phosphane-κ P)copper(I) chloro-form monosolvate: crystal structure, Hirshfeld surface analysis and solution NMR measurements

Sang Loon Tan; Chien Ing Yeo; Peter J Heard; Geoffrey R Akien; Nathan R Halcovitch; Edward R T Tiekink

doi:10.1107/S2056989016017837

[ N, N-Bis(2-hy-droxy-eth-yl)di-thio-carbamato-κ²S, S']bis-(tri-phenyl-phosphane-κ P)copper(I) chloro-form monosolvate: crystal structure, Hirshfeld surface analysis and solution NMR measurements

Acta Crystallogr E Crystallogr Commun. 2016 Nov 15;72(Pt 12):1799-1805. doi: 10.1107/S2056989016017837. eCollection 2016 Dec 1.

Authors

Sang Loon Tan¹, Chien Ing Yeo¹, Peter J Heard², Geoffrey R Akien³, Nathan R Halcovitch³, Edward R T Tiekink¹

Affiliations

¹ Research Centre for Crystalline Materials, Faculty of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia.
² Office of the Provost, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia.
³ Department of Chemistry, Lancaster University, Lancaster LA1 4YB, UK.

Abstract

The title compound, [Cu(C₅H₅NO₂S₂)(C₁₈H₁₅P)₂]·CHCl₃, features a tetra-hedrally coordinated Cu^I atom within a P₂S₂ donor set defined by two phosphane P atoms and by two S atoms derived from a symmetrically coordinating di-thio-carbamate ligand. Both intra- and inter-molecular hy-droxy-O-H⋯O(hydroxy) hydrogen bonding is observed: the former closes an eight-membered {⋯HOC₂NC₂O} ring, whereas the latter connects centrosymmetrically related mol-ecules into dimeric aggregates via eight-membered {⋯H-O⋯H-O}₂ synthons. The complex mol-ecules are arranged to form channels along the c axis in which reside the chloro-form mol-ecules, being connected by Cl⋯π(arene) and short S⋯Cl [3.3488 (9) Å] inter-actions. The inter-molecular inter-actions have been investigated further by Hirshfeld surface analysis, which shows the conventional hydrogen bonding to be very localized with the main contributors to the surface, at nearly 60%, being H⋯H contacts. Solution NMR studies indicate that whilst the same basic mol-ecular structure is retained in solution, the tri-phenyl-phosphane ligands are highly labile, exchanging rapidly with free Ph₃P at room temperature.

Keywords: Hirshfeld surface analysis; NMR; copper; crystal structure; dithiocarbamate; hydrogen bonding.