A new structural motif for cadmium dithiocarbamates: crystal structures and Hirshfeld surface analyses of homoleptic zinc and cadmium morpholine dithiocarbamates

Abstract

The crystal and molecular structures of two homoleptic morpholine-derived dithiocarbamates of zinc, binuclear {Zn[S2CN(CH2CH2)2O)2]2}2 (1), and cadmium, one-dimensional coordination polymer {Cd[S2CN(CH2CH2)2O)2]2}2 (2), are described. In 1, a centrosymmetric binuclear molecule is found as there are equal numbers of chelating and bidentate bridging dithiocarbamate ligands; weak transannular Zn···S interactions are found within the resultant eight-membered {···SCSZn}2 ring which has the form of a chair. The resultant 4+1 S5 donor set is highly distorted with the geometry tending towards a square-pyramid. By contrast, a square-planar geometry is found in centrosymmetric 2 defined by symmetrically chelating dithiocarbamate ligands. The presence of Cd···S secondary bonding in the crystal of 2 leads to a distorted 4+2 S6 octahedron and a linear coordination polymer, which is unprecedented in the structural chemistry of cadmium dithiocarbamates. The analyses of the Hirshfeld surfaces for 1 and 2 show the dominance of H···H, S···H/H···S and O···H/H···O contacts to the surface, i.e. contributing around 90 and 80%, respectively.

Crystal structure of catena-poly[{μ2-1,5-bis(diphenylphosphanyl)pentane-κ2 P:P′}dichloridocadmium(II)], C29H30CdCl2P2

“…As anticipated, the cadmium atom is tetrahedrally coordinated within a Cl 2 P 2 donor set. The Cd-Cl1, Cl2 bond lengths of 2.4359 (10) As indicated in the figure, the dppp ligands are µ 2 -bridging so that a one-dimensional coordination polymer results. The chain is propagated by translational symmetry along the baxis so it has a linear topology, as shown in the lower view of the figure (all hydrogen atoms have been omitted).…”

“…Prior to the most recent study [5], the only other polymeric structure was that formed between CdCl 2 and (R,R)-trans-4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxalane [8]. The title one-dimensional coordination polymer [CdCl 2 (dppp)]n, (I), where dppp is 1,5-bis (diphenylphosphino)propane, was determined in continuation of on-going studies of cadmium coordination polymers [5,[9][10][11]. The asymmetric unit of (I) is shown in the top view of the figure (70% probability displacement ellipsoids; the unlabelled dppp molecule is related by the symmetry operation (i) x, −1 + y, z) and comprises a cadmium(II), two chlorido ligands and a full dppp ligand.…”

Crystal structure of tetrakis (N-(2-hydroxyethyl)-N-isopropylcarbamodithioato-κS,S′)-(μ2(2-(pyridin-4-yl)vinyl)pyridine-κN,N′)dicadmium(II), C36H58Cd2N6O4S8

“…In common with most cadmium dithiocarbamate, Cd(S 2 CNRR′) 2 , structures [6], the species with R = isopropyl and R′ = CH 2 CH 2 OH is known to associate into a dimer formulated as [Cd(S 2 CN(iPr)CH 2 CH 2 OH) 2 ] 2 as a result of equal numbers of tridentate-µ 2 -and chelating-dithiocarbamate ligands leading to five-coordinate Cd centres [5,7]. However, a kinetic form has also been characterised for this compound [5,7] which is a rare example of a one-dimensional coordination polymer for cadmium dithiocarbamates [5][6][7][8]. Experiments show the polymers to convert to the dimeric form with the egress of time.…”

Snap Frozen! Capturing Two Metastable Polymorphs in a Tetramorphic One-Dimensional Coordination Polymer Constructed from Cadmium, Dithiophosphate, and 4-Pyridinealdazine

“…The one-dimensional coordination polymer {Cd­[S 2 P­(OMe) 2 ] 2 (4-pyridine-aldazine)} n ( 1 ) became available during the course of ongoing studies into the rationalization of the formation/topology of coordination polymers of the zinc-triad 1,1-dithiolates (e.g., dithiocarbamate, – S 2 CNR 2 , xanthate, – S 2 COR, and dithiophosphate, – S 2 P­(OR) 2 ) − and their complexes with potentially bridging bipyridyl-type molecules. − In the case of 1 , temperature-dependent polymorphism was observed (single crystal, PXRD, and DSC): at room temperature, an 1α form was observed which, upon cooling, underwent a SCSC transformation to a 1β form which remained until 100 K. When crystals of 1 were placed directly into the cold stream at 100 K, three different forms were found, i.e., 1β , 1γ , and 1δ . Heating 1β gave 1α , and heating each of 1γ and 1δ gave 1β , and then 1α .…”