Synthesis and structural characterization of two new polynuclear metal thiosaccharinates: Hexakis (thiosaccharinato) hexasilver (I) and tetrakis (thiosaccharinato) …
M Dennehy, GP Tellería, SH Tarulli, OV Quinzani… - Inorganica chimica …, 2007 - Elsevier
M Dennehy, GP Tellería, SH Tarulli, OV Quinzani, SD Mandolesi, JA Guida, GA Echeverría…
Inorganica chimica acta, 2007•ElsevierThe title compounds, for short Ag6 (tsac) 6 (1) and [Cu4 (tsac) 4 (MeCN) 2]· 2MeCN (2), were
prepared by the reaction of thiosaccharin with Ag (I) or Cu (II) salts in different solvents. The
new complexes were characterized by FT-IR, Raman, UV–Vis and NMR spectroscopy. Their
crystal and molecular structures were determined by X-ray diffraction methods. The
structures were solved from 1621 (1) and 7080 (2) reflections with I> 2σ (I) and refined to
agreement R1-factors of 0.0261 (1) and 0.0456 (2). Ag6 (tsac) 6 molecule derives from the …
prepared by the reaction of thiosaccharin with Ag (I) or Cu (II) salts in different solvents. The
new complexes were characterized by FT-IR, Raman, UV–Vis and NMR spectroscopy. Their
crystal and molecular structures were determined by X-ray diffraction methods. The
structures were solved from 1621 (1) and 7080 (2) reflections with I> 2σ (I) and refined to
agreement R1-factors of 0.0261 (1) and 0.0456 (2). Ag6 (tsac) 6 molecule derives from the …
The title compounds, for short Ag6(tsac)6 (1) and [Cu4(tsac)4(MeCN)2]·2MeCN (2), were prepared by the reaction of thiosaccharin with Ag(I) or Cu(II) salts in different solvents. The new complexes were characterized by FT-IR, Raman, UV–Vis and NMR spectroscopy. Their crystal and molecular structures were determined by X-ray diffraction methods. The structures were solved from 1621 (1) and 7080 (2) reflections with I>2σ(I) and refined to agreement R1-factors of 0.0261 (1) and 0.0456 (2). Ag6(tsac)6 molecule derives from the clustering of six Ag(tsac) moieties related to each other through the crystallographic 3-bar (S6) symmetry operations of the R3¯ space group. This results in a highly regular molecular structure where the silver atoms are at the corners of an octahedral core slightly compressed along one of its three-fold axis [inter-metallic Ag⋯Ag contacts of 3.1723(4) and 3.1556(4)Å]. The six thiosaccharinate ligands bridge neighboring Ag atoms along the C3-axis through Ag–N bonds [d(Ag–N)=2.285(2)Å] at one end and bifurcated Ag–S(thione)–Ag bonds [Ag–S distances of 2.4861(7) and 2.5014(8)Å] at the other end. In contrast, the 2 compound is arranged in the lattice as an irregular tetrameric copper complex [Cu4(tsac)4(MeCN)2] where the metals show different environments. Two copper ions are four-fold coordinated to three tsac ions through the N-atom of one tsac [Cu–N distances of 2.112(3) and 2.064(3)Å] and the thione sulfur atom of the other two [Cu–S distances in the range from 2.284(1) to 2.358(1)Å] and to a MeCN solvent molecule [Cu–N distances of 1.983(4) and 2.052(3)Å]. The other two copper ions are in three-fold environment, one trans-coordinated to two tsac ions [Cu–N distances of 1.912(3) and 1.920(3)Å] and to the thione S-atom of a third ligand [d(Cu–S)=2.531(1)Å], the other one to the thione sulfur atom of three tsac ligands [Cu–S distances in the range from 2.229(1) to 2.334(1)Å]. The clustering renders the metals to short distances from each other, the shorter Cu⋯Cu distance being 2.6033(7)Å, as to presume the existence of weak inter-metallic interaction within the cluster.
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