Steric control over C=O...C=O interactions in M(S₂COR)₂(dafone) compounds: M = Zn and Cd; R = Me, Et and iPr; dafone = 4,5-diazafluoren-9-one-N,N′

Abstract

Crystallography shows that with the smaller xanthate-bound methyl groups in Zn(S2COMe)2(dafone) (1) and Cd(S2COMe)2(dafone) (3) anti-parallel C=O…C=O interactions link molecules into dimers. These are further associated via π—π interactions into a supramolecular chain, and in the case of 3 into a supramolecular two-dimensional array via C—H…S contacts. Increasing the size of the organic residue, i.e. to ethyl and isopropyl in Zn(S2COEt)2(dafone) (2), Cd(S2COEt)2(dafone) (4) and Cd(S2CO-iPr)2(dafone) (5), does not allow for the formation of this supramolecular architecture. Instead, supramolecular chains are sustained by C—H…S and C—H…π(chelate) interactions (the latter exclusively in the case of 5). The presence of recognisable/significant π—π and C—H…S and C—H…π(chelate) interactions is not consistent amongst the series yet only two crystal packing patterns are noted depending on the presence of the C=O…C=O interactions. This observation points to the importance of overall crystal packing considerations of binuclear species in 1 and 3, and mononuclear species in 2, 4 and 5.

Aerosol-Assisted Chemical Vapor Deposition of CdS from Xanthate Single Source Precursors

“…As was also the case for 1 , both compounds 2 and 3 adopt a cis, cis, cis-configuration of ligands about the octahedrally coordinated metals. Although a majority of the known six-coordinate cadmium xanthate structures comprise bidentate donor coligands and, thus, are constrained to a similar cisoid configuration, − the structures of 1 – 3 contrast with the only other reported cadmium xanthate species incorporating two monodentate donors, [ trans -Cd­(S 2 COBu- n ) 2 ­(C 5 H 5 N) 2 ], in which the pyridine ligands adopt a mutual trans disposition . Despite this adjustment, the various Cd–S bond lengths vary across a similar range to that established for these previously reported compounds (ca.…”

Serendipitous compositional and structural diversity in urotropine adducts of binary cadmium xanthates

“…In fact, there is only one example of structurally characterised cadmium xanthate with bridging bipyridine-type ligands, namely [Cd(S2COiPr)2(4,4ꞌ-bipy)]n, which is a linear polymer [46], even though structures with bidentate bipyridine donors are well known [47][48][49]. A linear coordination polymer is also noted in the structure of {Cd[S2CN(CH2Ph)2]2(4,4ꞌ-bipy)}n [50].…”