Abstract
The common structural feature of the title compounds, [Zn(C4H8NOS2)2(C5H5N)]·C5H5N (I) and [Zn(C5H10NOS2)2(C5H5N)]·C5H5N (II), which differ by having di-thio-carbamate N-bound methyl (I) and ethyl (II) groups, is the coordination of each ZnII atom by two non-symmetrically chelating di-thio-carbamate ligands and by a pyridine ligand; in each case, the non-coordinating pyridine mol-ecule is connected to the Zn-containing mol-ecule via a (hy-droxy)O-H⋯N(pyridine) hydrogen bond. The resulting NS4 coordination geometry is closer to a square-pyramid than a trigonal bipyramid in the case of (I), but almost inter-mediate between the two extremes in (II). The mol-ecular packing features (hy-droxy)O-H⋯O(hy-droxy) hydrogen bonds, leading to supra-molecular chains with a zigzag arrangement along [10-1] (I) or a helical arrangement along [010] (II). In (I), π-π [inter-centroid distances = 3.4738 (10) and 3.4848 (10) Å] between coordinating and non-coordinating pyridine mol-ecules lead to stacks comprising alternating rings along the a axis. In (II), weaker π-π contacts occur between centrosymmetrically related pairs of coordinating pyridine mol-ecules [inter-centroid separation = 3.9815 (14) Å]. Further inter-actions, including C-H⋯π(chelate) inter-actions in (I), lead to a three-dimensional architecture in each case.
Highlights
The common structural feature of the title compounds, [Zn(C4H8NOS2)2(C5H5N)]ÁC5H5N (I) and [Zn(C5H10NOS2)2(C5H5N)]ÁC5H5N (II), which differ by having dithiocarbamate N-bound methyl (I) and ethyl (II) groups, is the coordination of each ZnII atom by two non-symmetrically chelating dithiocarbamate ligands and by a pyridine ligand; in each case, the non-coordinating pyridine molecule is connected to the Zn-containing molecule via aO—HÁ Á ÁN(pyridine) hydrogen bond
In order to overcome the reluctance of zinc(II) dithiocarbamates to generate extended supramolecular architectures, the dithiocarbamate ligands can be functionalized with hydrogen-bonding potential, i.e. ÀS2CN(R)CH2CH2OH (Howie et al, 2008), and systematic studies conducted
This influence is nicely seen in the crystal of the binary species, Zn[S2N(CH2CH2OH)2]2, where the dimeric aggregate, mediated by Zn—S bridges, self-assembles into a three-dimensional architecture based on hydrogen bonding (Benson et al, 2007)
Summary
Multidentate ligands such as dithiocarbamate, ÀS2CNRR0, dithiocarbonate (xanthate), ÀS2COR, and dithiophosphate, ÀS2P(OR)(OR0), all belong to the 1,1-dithiolate class of ligands. When an excess of bpe is introduced into the reaction with R = Et, the dimeric aggregate is again isolated and an additional molecule of bpe is incorporated into the crystal (Lai & Tiekink, 2003) This contrasting behaviour can be explained in terms of an effective chelating mode of the dithiocarabmate ligand owing to a 40% contribution of the 2ÀS2C N+RR0 canonical form to the overall electronic structure. In order to overcome the reluctance of zinc(II) dithiocarbamates to generate extended supramolecular architectures, the dithiocarbamate ligands can be functionalized with hydrogen-bonding potential, i.e. ÀS2CN(R)CH2CH2OH (Howie et al, 2008), and systematic studies conducted This influence is nicely seen in the crystal of the binary species, Zn[S2N(CH2CH2OH)2]2, where the dimeric aggregate, mediated by Zn—S bridges, self-assembles into a three-dimensional architecture based on hydrogen bonding (Benson et al, 2007). 1247 Poplaukhin and Tiekink [Zn(C4H8NOS2)2(C5H5N)]ÁC5H5N and its N-ethyl analogue
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