Supramolecular Isomerism in a Cadmium Bis(N-Hydroxyethyl, N-isopropyldithiocarbamate) Compound: Physiochemical Characterization of Ball (n = 2) and Chain (n = ∞) Forms of {Cd[S₂CN(iPr)CH₂CH₂OH]₂·solvent}_n

Abstract

were harvested from a dry acetonitrile solution of Cd[S 2 CN(iPr)-CH 2 CH 2 OH] 2 after one or two days and proved to be a coordination polymer in which all dithiocarbamate ligands are μ 2 ,κ 2 -tridentate, bridging two cadmium atoms and simultaneously chelating one of these. If the same solution was allowed to stand for at least several days, 2 is replaced by blocks comprising a supramolecular isomer of 2, dimeric 1, with formula {Cd[S 2 CN(iPr)CH 2 CH 2 OH] 2 } 2 •2H 2 O•2MeCN, and two ligands coordinating μ 2 ,κ 2 as in 2 and the other two purely κ 2 -chelating. The time dependency correlates with the pivotal role of water in driving the conversion of "chain" 2 to "ball" 1; crystals of 2 could not be isolated from "wet" acetonitrile. When each of 1 and 2 are dissolved in solution, they exhibit comparable spectroscopic attributes ( 1 H, 13 C, and 113 Cd NMR and UV/vis), indicating the solution structures are the same. Both 1 and 2 are luminescent in the solid state with 1 being significantly brighter than 2. Greenockite CdS nanoparticles are generated by the thermal decomposition of both 1 and 2.

Crystal structure of 3-(propan-2-yl)-1,3-oxazolidine-2-thione, C6H11NOS

“…Functionalised dithiocarbamate ligands such as those containing hydroxyethyl groups, being capable of hydrogen bonding, offer opportunities in crystal engineering [1][2][3][4]. During the course of recent studies [4], it was noted that decomposition/cyclisation of -S 2 CN(iPr)CH 2 CH 2 OH occurred during the synthesis of metal complexes.…”

“…During the course of recent studies [4], it was noted that decomposition/cyclisation of -S 2 CN(iPr)CH 2 CH 2 OH occurred during the synthesis of metal complexes. Subsequently, it was possible to prove this reaction wasb ase-mediated as outlined in "Sourceo fM aterial".T he oxazolidine ring is close to planar with the deviations from the least-squares plane being -0.0582(11), 0.0563(13), 0.0012 (14), 0.0930 (17) and -0.0923(16) Åfor the O1, N1 and C1-C3 atoms, respectively.T he angles aboutthe C1 atom arenon-symmetrical ranging from 110.96(12)°for N1-C1-O1 to 128.70(11)°for N1-C1-S1, reflecting the influence of thel arger thione-S (C1=S1 =1.6680(15) Å) atom.…”

Mono urotropine adducts of some binary zinc xanthates and dithiocarbamates: solid-state molecular structures and supramolecular self-assembly

“…With this background in mind, it was thought of interest to continue these studies with binary zinc xanthates which resulted in the characterisation of I and II, Figure 1. In addition, studies were performed with related zinc dithiocarbamates leading to III and IV, Figure 1, as these have proven to provide interesting supramolecular chemistry owing to their potential for forming hydrogen bonding interactions [9][10][11][12]. Herein, the crystal and molecular structures of I-IV are described.…”

Exploring the crystallization landscape of cadmium bis(N-hydroxyethyl, N-isopropyldithiocarbamate), Cd[S2CN(iPr)CH2CH2OH]2

“…However, this situation changed in 2013 with the report of a coordination polymer, [{Cd[S2CN(iPr)CH2CH2OH]2}3·MeCN]∞ [50].…”

“…For completeness, it is noted that the nonalkyl species, {Cd[S2CN(H)R]2}∞ R = n-C5H11 and n-C12H25, are linear coordination polymers with octahedrally coordinated cadmium atoms [52]. (37) mother liquor over a period of several days it transformed to {Cd[S2CN(iPr)CH2CH2OH]2}2·2H2O·2MeCN, which has the normally adopted binuclear motif [50]. The conversion from the polymer to dimeric form was proposed to be mediated by adventitious water [50].…”