[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

Abstract

A distorted octa­hedral cis-N2S4 coordination geometry is found in the title solvated bimetallic complex. The packing features supra­molecular layers sustained by O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonding.

Crystal Chemistry of Zinc, Cadmium and Mercury

“…There is a sole example of a cadmium xanthate structure, [Cd(S 2 COiPr) 2 (bpy)] n (58) [74], making xanthates the least represented of the conventional 1,1-dithiolate ligands included in this review; data for all 31 cadmium structures, that is, 58-88 [62,[74][75][76][77][78][79][80][81][82][83][84][85][86][87][88][89][90][91][92], are listed in Table 2. There are two independent formula units in the crystal and each of these is disposed about a two-fold axis of asymmetry with the cadmium and nitrogen atoms lying on the axis.…”

“…However, the isolation of these species raises questions relating to the relative importance of coordinate-bond formation versus hydrogen bonding interactions and, therefore, these are of fundamental interest. The molecular structures of {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 (bpy)} 2 (85) [69], co-crystallised with half a bpy molecule, {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 (bpe) 3 (86) [90], {Cd[S 2 CN(nPr)CH 2 CH 2 OH] 2 }(4-pyald) 2 (87) [91] and {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 (3-pyald) 2 (88) [92] are illustrated in Figure 21a-d. In 85, which features a monodentate bpy ligand, the cadmium atom is five-coordinate within a NS 4 donor set that defines a geometry approaching trigonal-bipyramidal (τ = 0.67) with the less tightly bound sulphur atoms defining the axial positions.…”

Perplexing Coordination Behaviour of Potentially Bridging Bipyridyl-Type Ligands in the Coordination Chemistry of Zinc and Cadmium 1,1-Dithiolate Compounds

“…There is a sole example of a cadmium xanthate structure, [Cd(S2COiPr)2(bpy)]n (58) [74], making xanthates the least represented of the conventional 1,1-dithiolate ligands included in this review; data for all 31 cadmium structures, that is, 58-88 [62,[74][75][76][77][78][79][80][81][82][83][84][85][86][87][88][89][90][91][92], are listed in Table 2. There are two independent formula units in the crystal and each of these is disposed about a two-fold axis of asymmetry with the cadmium and nitrogen atoms lying on the axis.…”

“…However, the isolation of these species raises questions relating to the relative importance of coordinate-bond formation versus hydrogen bonding interactions and, therefore, these are of fundamental interest. The molecular structures of {Cd[S2CN(iPr)CH2CH2OH]2(bpy)}2 (85) [69], co-crystallised with half a bpy molecule, {Cd[S2CN(iPr)CH2CH2OH]2}2(bpe)3 (86) [90], {Cd[S2CN(nPr)CH2CH2OH]2}(4-pyald)2 (87) [91] and {Cd[S2CN(iPr)CH2CH2OH]2}2(3-pyald)2 (88) [92] are illustrated in Figure 21a-d. In 85, which features a monodentate bpy ligand, the cadmium atom is five-coordinate within a NS4 donor set that defines a geometry approaching trigonal-bipyramidal (τ = 0.67) with the less tightly bound sulphur atoms defining the axial positions.…”

“…Here, it is pertinent to note that the stoichiometry of the reactants in these reactions with functionalised dithiocarbamate ligands does not necessarily determine the synthetic outcome. For example, crystals of 86 can be isolated from solutions containing 2:1, 1:1 and 1:2 ratios of "Cd[S 2 N(iPr)CH 2 CH 2 OH] 2 " and bpe [90].…”