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

Abstract

Abstract:The crystal chemistry of the zinc-triad binary 1,1-dithiolates, that is, compounds of xanthate [ − S 2 COR], dithiophosphate [ − S 2 P(OR) 2 ], and dithiocarbamate [ − S 2 CNR 2 ] ligands, is reviewed. Owing to a wide range of coordination modes that can be adopted by 1,1-dithiolate anions, such as monodentate, chelating, µ 2 -bridging, µ 3 -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.

Crystal structure of catena-[(bis(O,O′-diethyl dithiophosphato-S,S′)-μ2-1,2-bis(3-pyridylmethylene)hydrazine-N,N′)zinc(II)], {C20H30N4O4P2S4Zn}n

“…When 3-PyAld is employed and the 1,1-dithiolate ligand is dithiophosphate [ − S 2 P(OR) 2 ], bidentate bridging is found in {Zn[S 2 P(O-iPr) 2 ] 2 (3-PyAld)}n, (I), which is a one-dimensional coordination polymer with a step-ladder topology [7]. In the present report, the crystal and molecular structures of the ethyl analogue of the latter is described as it is well documented in the structural chemistry of the zinc-triad 1,1-dithiolates that changes in R groups can have profound implications on the ultimate structural motif adopted in the solid-state [5,8].…”

Crystal structure of catena-poly[(μ2-1,2-bis(3-pyridylmethylene)hydrazine-κ2 N:N′)-bis(O,O′-dimethyl dithiophosphato-κ2-S,S′)cadmium(II)], {C16H22CdN4O4P2S4}n

“…It is well-documented that very different structures/supramolecular architectures can be observed for the zinc-triad 1,1-dithiolates [5] and their adducts with bipyridyltype ligands [6] when only small changes in the nature of a remote group are made. This has been very recently highlighted in the structures of {Cd[S 2 P(OR) 2 ] 2 (pyrazine)}n. Thus, in the case of R = Et, an octahedral trans-N 2 S4 donor set is found for cadmium(II) within a linear, one-dimensional coordination polymer [7].…”

Crystal structure of (4-fluorobenzyl-κC)(bis(2-hydroxyethyl) carbamodithioato-κ2 S,S′)(2,2′-imino-diethanolato-κ3 N,O,O′)tin(IV), C16H25FN2O4S2Sn

“…The 1,1-dithiolate, e.g. dithiocarbamate ( − S 2 CNR 2 ), compounds of the zinc-triad elements [5], main group elements [6,7], including tin [8], are well-known to form secondary M• • • S bonding interactions in their crystal structures [9,10]. However, when concurrently bound to potentially bidentate, bridging bi-pyridyl ligands, with the aim of increasing the dimensionality of the supramolecular association, the secondary bonding is generally lost, as amply demonstrated in the structural chemistry of the zinc-triad 1,1-dithiolates [11].…”

“…One way of overcoming this limitation is to introduce hydrogen bonding functionality in the R groups, e.g. hydroxyethyl groups, as the resultant hydrogen bonding can lead to one-, two-and, sometimes, three-dimensional aggregation in the solid-state [5][6][7][8]11]. In the title mixed ligand, organotin compound, (4-FC 6 H4CH 2 )Sn[OCH 2 CH 2 N(H)CH 2 CH 2 O][S 2 CN(CH 2 CH 2 OH) 2 ], (I), the dithiocarbamate ligand bears two hydroxyethyl groups, each capable of hydrogen bonding.…”

“…CrysAlis PRO [1], SHELX [2,3], WinGX/ORTEP [4] Di(4-fluorobenzyl)tin dichloride was synthesized by the direct reaction of 4-fluorobenzyl chloride (Merck) and metallic tin powder (Merck) in toluene according to a literature procedure [5]. The dithiocarbamate ligand was prepared in situ (methanol; 15 mL) from the reaction of CS 2 (Merck, 0.25 mmol) with diethanolamine (Merck, 0.25 mmol) and NaOH (0.02 mL; 50% w/v); CS 2 was added dropwise into the methanol solution.…”