New cadmium chloride complexes with imidazolidine-2-thione and its derivatives: X-ray structures, solid state and solution NMR and antimicrobial activity studies

The crystal chemistry of the zinc-triad binary 1,1-dithiolates, that is, compounds of xanthate [−S2COR], dithiophosphate [−S2P(OR)2], and dithiocarbamate [−S2CNR2] ligands, is reviewed. Owing to a wide range of coordination modes that can be adopted by 1,1-dithiolate anions, such as monodentate, chelating, μ2-bridging, μ3-bridging, etc., there exists a rich diversity in supramolecular assemblies for these compounds, including examples of zero-, one-, and two-dimensional architectures. While there are similarities in structural motifs across the series of 1,1-dithiolate ligands, specific architectures are sometimes found, depending on the metal centre and/or on the 1,1-dithiolate ligand. Further, an influence of steric bulk upon supramolecular aggregation is apparent. Thus, bulky R groups generally preclude the close approach of molecules in order to reduce steric hindrance and therefore, lead to lower dimensional aggregation patterns. The ligating ability of the 1,1-dithiolate ligands also proves crucial in determining the extent of supramolecular aggregation, in particular for dithiocarbamate species where the relatively greater chelating ability of this ligand reduces the Lewis acidity of the zinc-triad element, which thereby reduces its ability to significantly expand its coordination number. Often, the functionalisation of the organic substituents in the 1,1-dithiolate ligands, for example, by incorporating pyridyl groups, can lead to different supramolecular association patterns. Herein, the diverse assemblies of supramolecular architectures are classified and compared. In all, 27 structurally distinct motifs have been identified.

https://www.mdpi.com/2073-4352/8/7/292/pdf

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

Structural characterization and AC conductivity of bis tetrapropylammonium hexachlorado-dicadmate, [N(C3H7)4]2Cd2Cl6

Fixation modes of gold(III) from solutions using cadmium(II) dithiocarbamates. Preparation, supramolecular structure and thermal behaviour of polynuclear and heteropolynuclear gold(III) complexes: Bis(N,N-dialkyldithiocarbamato-S,S′)gold(III) polychlorometallates, [Au(S2CNR2)2]nX (n = 1: X = [AuCl4]−; n = 2: X = [CdCl4]2−, [Cd2Cl6]2−)

Crystallization of Cd[S2CN(iPr)CH2CH2OH]2 from
ethanol yields the coordination polymer [{Cd[S2CN(iPr)
CH2CH2OH]2}·EtOH]∞ (1) within 3 h. When the solution is
allowed to stand for another hour, the needles begin to
dissolve and prisms emerge of the supramolecular isomer
(SI), binuclear {Cd[S2CN(iPr)CH2CH2OH]2}2·2EtOH (2).
These have been fully characterized spectroscopically
and by X-ray crystallography. Polymeric 1 has 2-fold symmetry
and features dithiocarbamate ligands coordinating
two octahedral Cd atoms in a μ2κ2-tridentate mode.
Binuclear 2 is centrosymmetric with two ligands being
μ2κ2-tridentate as for 1 but the other two being κ2-chelating
leading to square pyramidal geometries. The conversion
of the kinetic crystallization product, 1, to thermodynamic
2 is irreversible but transformations mediated by recrystallization
(ethanol and acetonitrile) to related literature
SI species, namely coordination polymer [{Cd[S2CN(iPr)
CH2CH2OH]2}3·MeCN]∞ and binuclear {Cd[S2CN(iPr)CH2CH
2
OH]2}2·2H2O·2MeCN, are demonstrated, some of which
are reversible. Three other crystallization outcomes are
described whereby crystal structures were obtained for
the 1:2 co-crystal {Cd[S2CN(iPr)CH2CH2OH]2}2:2[3-(propan-
2-yl)-1,3-oxazolidine-2-thione] (3), the salt co-crystal [iPr
NH2(CH2CH2OH)]4[SO4]2{Cd[S2CN(iPr)CH2CH2OH]2}2 (4) and
the salt [iPrNH2(CH2CH2OH)]{Cd[S2CN(iPr)CH2CH2OH]3} (5).
These arise as a result of decomposition/oxidation of the
dithiocarbamate ligands. In each of 3 and 4 the binuclear
{Cd[S2CN(iPr)CH2CH2OH]2}2 SI, as in 2, is observed strongly
suggesting a thermodynamic preference for this form.

/pdf/exploring-the-crystallization-landscape-of-cadmium-bis-n-431zloh6oe.pdf

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

Conformational isomerism of the binuclear N,N-pentamethylenedithiocarbamate cadmium(II) complex, [Cd2{S2CN(CH2)5}4] on multinuclear (15N, 113Cd) CP/MAS NMR and single-crystal X-ray diffraction data

Alexey A. Konzelko

Papers

Conformational isomerism of the binuclear N,N-pentamethylenedithiocarbamate cadmium(II) complex, [Cd2{S2CN(CH2)5}4] on multinuclear (15N, 113Cd) CP/MAS NMR and single-crystal X-ray diffraction data