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Edward R. T. Tiekink, M.J. Cox
Structural features of zinc(II) bis(O-alkyldithio-carbonate) and zinc(II) bis(N,N-dialkyldithiocarbamate) compounds
The crystal and molecular structures of three compounds, [Zn(S2COnBu)2], [Zn(S2CN(Et)Cy)2] and [Zn(S2CNCy2)2] have been determined. The colorless crystals of [Zn(S2COnBu)2], obtained as a 0.75C6H6 solvate and investigated at room temperature, are triclinic, space group P- 1 with unit cell dimensions a= 12.885(5)Å, b=18.72(1)Å, c=8.564(3)Å, α =96.54(4)°, β = 102.48(3)°, γ = 87.33(4)°, Z=4 and Dx=1.645Mgm-3. The colorless crystals of [Zn(S2CN(Et)Cy)2], investigated at 200K, are monoclinic, space group P21/c with unit cell dimensions a=8.618(5)Å, b=16.500(4)Å, c= 16.242(2) Å, β = 97.70(2)°, Z = 4 and Dx = 1.364 Mg m-3. Crystals of colorless [Zn(S2CNCy2)2] (110K) are trigonal, space group P3221 with unit cell dimensions a= 10.264(10)Å, c=23.630(9)Å, Z=3 and Dx= 1.343Mgm-3. The structures were solved by direct methods and each refined by a full-matrix least-squares procedure to final R=0.058 using 3135 reflections for [Zn(S2COnBu)2]; to R=0.037 using 3282 reflections for [Zn(S2CN(Et)Cy)2]; and to final R=0.041 for 952 reflections for [Zn(S2CNCy2)2]. The structure of [Zn(S2COnBu)2] is cyclotetrameric, being based on a square of zinc atoms with each edge bridged by a bidentate bridging xanthate ligand. The remaining sites in the distorted tetrahedral geometry about each zinc atom is completed by a chelating ligand. A dimeric structure, arising from the presence of two bidentate bridging dithiocarbamate ligands, is found in the structure of [Zn(S2CN(Et)Cy)2] where, again, the distorted tetrahedral geometry about each zinc atom is completed by a chelating ligand. In contrast to oligomeric structures found for [Zn(S2COnBu)2] (16-membered ring) and [Zn(S2CN(Et)Cy)2] (8-membered ring), a monomeric structure with a distorted tetrahedral geometry about the zinc atom is found for [Zn(S2CNCy2)2]. An analysis of the diverse structural chemistry of these and related zinc bis xanthate and zinc bis dithiocarbamate compounds is presented.
Zeitschrift für Kristallographie, Oldenbourg Wissenschaftsverlag
Print ISSN: 0044-2968
Volume: 214, 03/1999
Pages: 184