The remarkable propensity for the formation of C-H π(chelate ring) interactions in the crystals of the first-row transition metal dithiocarbamates and the supramolecular architectures they sustain

• Published in: CrystEngComm 2020-11, Vol.22 (43), p.738-7333
• Main Author: Tiekink, Edward R. T
• Format: Article
• Language: English
• Subjects: Aromatic compounds; Chelates; Crystallography; Crystals; Electronegativity; Hydrogen atoms; Transition metals
• ISSN: 1466-8033; 1466-8033
• DOI: 10.1039/d0ce00289e

The Cambridge Crystallographic Database has been searched for the presence of intermolecular C-H π(chelate ring) interactions, known to be stabilising, in the crystals of the first-row transition metal dithiocarbamates, i.e. containing anionic ligands of the type − S 2 CNR 2 , R = H, alkyl and aryl. A significant propensity to form C-H π(chelate ring) interactions is noted, especially in crystals of nickel and copper dithiocarbamates. The participating hydrogen atoms are characterised as being near an electronegative atom/substituent encouraging their engagement in this supramolecular synthon. The survey shows that an open, square-planar geometry is not a prerequisite for a C-H π(chelate ring) interaction but, allows, on average, more of these contacts leading to one- and two-dimensional architectures. It is concluded that a search for a C-H π(chelate ring) supramolecular synthon should be included in any detailed analysis of the molecular packing of metal-containing crystals. C-H π(chelate ring) interactions play an important role in assembling first-row transition metal dithiocarbamates in their crystals.