A new structural motif for cadmium dithiocarbamates: Crystal structures and Hirshfeld surface analyses of homoleptic zinc and cadmium morpholine dithiocarbamates

Jimmy Ahmad, and How, Fiona N. F. and Siti Nadiah Abdul Halim, and Jotani, Mukesh M. and Lee, See Mun * and Tiekink, Edward R. T. * (2019) A new structural motif for cadmium dithiocarbamates: Crystal structures and Hirshfeld surface analyses of homoleptic zinc and cadmium morpholine dithiocarbamates. Zeitschrift fur Kristallographie, 234 (5). pp. 341-349. ISSN 0044-2968 (In Press)

Text Tiekink New Structural motif for cadmium Z. Kristallogr. 243 2019 341 accepted.pdf - Accepted Version Restricted to Repository staff only Available under License Creative Commons Attribution Non-commercial. Download (1MB) | Request a copy

Abstract

The crystal and molecular structures of two homoleptic morpholine-derived dithiocarbamates of zinc, binuclear {Zn[S2CN(CH2CH2)2O)2]2}2 (1), and cadmium, one-dimensional coordination polymer {Cd[S2CN(CH2CH2)2O)2]2}2 (2), are described. In 1, a centrosymmetric binuclear molecule is found as there are equal numbers of chelating and bidentate bridging dithiocarbamate ligands; weak transannular Zn...S interactions are found within the resultant eight-membered {...SCSZn}2 ring which has the form of a chair. The resultant 4+1 S5 donor set is highly distorted with the geometry tending towards a square-pyramid. By contrast, a square-planar geometry is found in centrosymmetric 2 defined by symmetrically chelating dithiocarbamate ligands. The presence of Cd...S secondary bonding in the crystal of 2 leads to a distorted 4+2 S6 octahedron and a linear coordination polymer, which is unprecedented in the structural chemistry of cadmium dithiocarbamates. The analyses of the Hirshfeld surfaces for 1 and 2 show the dominance of H…H, S…H/H…S and O…H/H…O contacts to the surface, i.e. contributing around 90 and 80%, respectively.

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