Bis[bis(N-2-hydroxyethyl,N-isopropyl-dithiocarbamato)mercury(II)]₂: crystal structure and Hirshfeld surface analysis

Abstract

Abstract. The presence of both κ 2 -chelating and µ2,κ 2

[μ2-trans-1,2-Bis(pyridin-4-yl)ethene-κ2N:N′]bis{[1,2-bis(pyridin-4-yl)ethene-κN]bis[N-(2-hydroxyethyl)-N-isopropyldithiocarbamato-κ2S,S′]cadmium} acetonitrile tetrasolvate: crystal structure and Hirshfeld surface analysis

“…Recent Hirshfeld surface analyses of zinc-triad hydroxyethylsubstituted dithiocarbamates has provided key insight into their molecular packing over and beyond hydrogen-bonding considerations. For example, the relatively unusual C-HÁ Á Á(chelate) interactions (Tiekink & Zukerman-Schpector, 2011) (Howie et al, 2009), are clearly delineated in the Hirshfeld analysis of the molecular packing (Jotani et al, 2016). In the present study, using Crystal Explorer 3.1 (Wolff et al, 2012), the Hirshfeld surfaces were mapped over d norm , shape-index, curvedness and electrostatic potential for the asymmetric unit of (I Fig.…”

Exploring the Topological Landscape Exhibited by Binary Zinc-triad 1,1-dithiolates

“…Hence, the coordination geometry is best described as being based on an S 4 + 1 arrangement. The values calculated for τ [50] indicate geometries tending towards square-pyramidal (τ = 0.0), with the minimum value of 0.01 being found for {Hg[S 2 CN(i-Pr)CH 2 CH 2 OH] 2 } 2 (174) [162], and with all other structures, but one, having t < 0.32. The exceptional structure, [Hg{S 2 CN[CH 2 (3-py)]CH 2 (2-ferrocenyl)} 2 ] 2 (178) [109], has a τ value of 0.52.…”

“…The familiar binuclear motif seen in the zinc and cadmium dithiocarbamates is adopted by 16 mercury dithiocarbamate structures, 163-178 [109,143,149,[153][154][155][156][157][158][159][160][161][162][163]. Being 2-fold symmetric, {Hg[S2CN(n-Bu)2]2}2 (165) [143] is assigned motif N, with the rest of the molecules being motif O.…”

“…There are non-systematic variations in the Hg-S bond lengths although the range of the Hg-S bond lengths is relatively narrow, as exemplified by the aforementioned {Hg[S 2 CN(Benzyl)CH 2 (2-furyl)] 2 } 2 (175) [158] structure, with two independent molecules, where the range of Hg-S bond lengths of 2.46 to 2.73 Å encompasses most of the Hg-S separations in the other structures, with two exceptions. Before discussing these, it is relevant to note the range of transannular interactions within the eight-membered {-HgSCS} 2 [162], whereby the transannular interactions are shorter than the bridging Hg-S bond to the symmetry-related mercury atom. Under these circumstances, these structures represent a transition from motif M to motif O, but are assigned to the latter as all Hg-S separations are less than the sum of the respective van der Waals radii.…”

“…Similarly, strictly mononuclear Hg[S 2 CN(i-Pr) 2 ] 2 (142) [149], motif M, in one polymorph can also adopt binuclear motif O in another, as in 164 [154]. [162], whereby the transannular interactions are shorter than the bridging Hg-S bond to the symmetryrelated mercury atom. Under these circumstances, these structures represent a transition from motif M to motif O, but are assigned to the latter as all Hg-S separations are less than the sum of the respective van der Waals radii.…”