CEQUINOR   05415
CENTRO DE QUIMICA INORGANICA "DR. PEDRO J. AYMONINO"
Unidad Ejecutora - UE
artículos
Título:
Synthesis and Structural Characterization of Two New Polynuclear Metal Thiosaccharinates:
Autor/es:
M. DENNEHY; G. P. TELLERÍA; S. H. TARULLI; O. V. QUINZANI; S. D. MANDOLESI, J. A. GUIDA, G. A. ECHEVERRÍA, O. E. PIRO, E. E. CASTELLANO
Revista:
INORGANICA CHIMICA ACTA
Editorial:
Elsevier
Referencias:
Lugar: Amsterdam; Año: 2006
ISSN:
0020-1693
Resumen:
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-visible and NMR spectroscopy. Their crystal and molecular structures were determined by X-ray diffraction methods. 16(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-visible and NMR spectroscopy. Their crystal and molecular structures were determined by X-ray diffraction methods. 11 crystallizes in the trigonal R-3 space group with a=b=24.970(1), c=7.9220(4) Å, a=120° and Z=18 molecules per unit cell, and 2 in the triclinic P-1 space group, with a=12.785(1), b=13.887(1), c=14.960(1) Å, α=105.25(1), b=95.80(1), g=114.55(1)º, and Z=2. 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 R-3 space group. This result 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 showa=120° and Z=18 molecules per unit cell, and 2 in the triclinic P-1 space group, with a=12.785(1), b=13.887(1), c=14.960(1) Å, α=105.25(1), b=95.80(1), g=114.55(1)º, and Z=2. 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 R-3 space group. This result 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 show2 in the triclinic P-1 space group, with a=12.785(1), b=13.887(1), c=14.960(1) Å, α=105.25(1), b=95.80(1), g=114.55(1)º, and Z=2. 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 R-3 space group. This result 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 showα=105.25(1), b=95.80(1), g=114.55(1)º, and Z=2. 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 R-3 space group. This result 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 show1) 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 R-3 space group. This result 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 show1) 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 R-3 space group. This result 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 show6) symmetry operations of the R-3 space group. This result 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 show3-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 show2 compound is arranged in the lattice as an irregular tetrameric copper complex [Cu4(tsac)4(MeCN)2] where the metals show4(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 intermetallic interaction within the cluster. 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 intermetallic interaction within the cluster.
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