Abstract
The title structures, [M(C6H12NOS2)2(C10H8N2)]·0.5C10H8N2, for M = Zn, (I), and Cd, (II), feature terminally bound 4,4'-bipyridyl ligands and non-coordinating 4,4'-bi-pyridyl mol-ecules, with the latter disposed about a centre of inversion. The coordination geometry about the metal atom is defined by two non-symmetrically chelating di-thio-carbamate ligands and a pyridyl N atom. The NS4 donor sets are distorted but, approximate to trigonal bipyramidal in each case. In the crystal, hy-droxy-O-H⋯O(hy-droxy) and hy-droxy-O-H⋯N(pyrid-yl) hydrogen bonds between the zinc-containing mol-ecules lead to a supra-molecular layer parallel to (100). The three-dimensional architecture arises as the layers are linked via methine-C-H⋯S, pyridyl-C-H⋯O(hy-droxy) and π-π [inter-centroid distance between coordinated pyridyl rings = 3.6246 (18) Å] inter-actions. Channels along the c-axis direction are occupied by the non-coordinating 4,4'-bipyridine mol-ecules, which are held in place by C-H⋯π(chelate ring) contacts.
Highlights
The title structures, [M(C6H12NOS2)2(C10H8N2)]Á0.5C10H8N2, for M = Zn, (I), and Cd, (II), feature terminally bound 4,40-bipyridyl ligands and noncoordinating 4,40-bipyridyl molecules, with the latter disposed about a centre of inversion
Channels along the c-axis direction are occupied by the non-coordinating 4,40-bipyridine molecules, which are held in place by C—HÁ Á Á(chelate ring) contacts
While bidentate bridging is normally observed in the structural chemistry of zinc(II) bis(N,N0-dialkyldithiocarbamate)s, these more often than not lead to binuclear species of the general formula [Zn(S2CNRR0)2]2(4,40-bipyridyl) as first observed in the archetypal compound [Zn(S2CNEt2)2]2(4,40-bipyridyl) (Zemskova et al, 1994) and in other compounds relevant to the present study, such as {Zn[S2CN(R)CH2CH2OH]2}2(4,40bipyridyl) for R = Me, Et and CH2CH2OH (Benson et al, 2007)
Summary
The ditopic ligand 4,40-bipyridyl is ubiquitous in coordination chemistry, usually providing bridges between metal centres to generate coordination polymers. The difference in chemistry between zinc and cadmium dithiocarbamates can be rationalized in terms of the larger size of cadmium versus zinc but, in terms of the reduced Lewis acidity of the zinc atom owing to the strong chelation mode of the dithiocarbamate ligand. This is true for cadmium whereby unusual coordination modes are found for. The crystal and molecular structures of two compounds, formulated as Zn[S2CN(iPr)CH2CH2OH]2(4,40-bipyridyl)Á0.5(4,40-bipyridyl) (I) and the cadmium analogue (II), are described, i.e. featuring monodentate and non-coordinating 4,40-bipyridine molecules. Some differences in molecular geometry are apparent, most notably in the degree of symmetry in the Cd—
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