TY - JOUR
T1 - Structure-directing influence of halide in mercury thiolate clusters
AU - Bharara, Mohan S.
AU - Bui, Thanhhoa H.
AU - Parkin, Sean
AU - Atwood, David A.
PY - 2005/8/8
Y1 - 2005/8/8
N2 - Under identical conditions, the reaction of 2-aminoethanethiol hydrochloride with HgX2 (X = Cl and Br) in water yielded discrete hexanuclear [Hg6Cl8(SCH2CH2NH 3)8)]Cl4·4H2O (1) and nonanuclear [Hg9Br15(SCH2CH2NH 3)9](Cl0.8-Br0.2)3 (2) complexes with unusual coordination environments. Compound 1 crystallizes as triclinic with a = 9.434-(2) Å, b = 10.999(2) Å, c = 13.675(7) Å, α = 92.9(7)°, β = 105.2(7)°, and γ = 96.9(7)°, whereas 2 is monoclinic with a = 14.162(3) Å, b = 8.009(16) Å, c = 19.604(4) Å, α = γ = 90.0°, and β = 92.7(3)°. In both cases, it is observed that the halide creates the secondary structure around trinuclear units (dimer in 1 and trimer in 2) through Hg-X bonding. Two independent types of Hg atoms (four- and five-coordinate in 1) and (three- and four-coordinate in 2) are observed. The geometry around Hg is quite variable with bridging thiolate and both bridging and terminal halides. The angles around Hg associated with the S atoms are more obtuse than expected from mercury(II) thiolates with a coordination number of more than 2. Intermolecular hydrogen bonding involving NH3+, water molecules, and the halide atoms is responsible for the three-dimensional network in both compounds. Relatively short Hg⋯Hg interactions in 1 (3.797 and 3.776 Å) and in 2 (3.605 and 3.750 Å) are also observed. The compounds have been characterized with the help of 1H and 13C NMR, UV-Vis, infrared, Raman, and mass spectrometry, thermogravimetric analysis, and single X-ray crystallography.
AB - Under identical conditions, the reaction of 2-aminoethanethiol hydrochloride with HgX2 (X = Cl and Br) in water yielded discrete hexanuclear [Hg6Cl8(SCH2CH2NH 3)8)]Cl4·4H2O (1) and nonanuclear [Hg9Br15(SCH2CH2NH 3)9](Cl0.8-Br0.2)3 (2) complexes with unusual coordination environments. Compound 1 crystallizes as triclinic with a = 9.434-(2) Å, b = 10.999(2) Å, c = 13.675(7) Å, α = 92.9(7)°, β = 105.2(7)°, and γ = 96.9(7)°, whereas 2 is monoclinic with a = 14.162(3) Å, b = 8.009(16) Å, c = 19.604(4) Å, α = γ = 90.0°, and β = 92.7(3)°. In both cases, it is observed that the halide creates the secondary structure around trinuclear units (dimer in 1 and trimer in 2) through Hg-X bonding. Two independent types of Hg atoms (four- and five-coordinate in 1) and (three- and four-coordinate in 2) are observed. The geometry around Hg is quite variable with bridging thiolate and both bridging and terminal halides. The angles around Hg associated with the S atoms are more obtuse than expected from mercury(II) thiolates with a coordination number of more than 2. Intermolecular hydrogen bonding involving NH3+, water molecules, and the halide atoms is responsible for the three-dimensional network in both compounds. Relatively short Hg⋯Hg interactions in 1 (3.797 and 3.776 Å) and in 2 (3.605 and 3.750 Å) are also observed. The compounds have been characterized with the help of 1H and 13C NMR, UV-Vis, infrared, Raman, and mass spectrometry, thermogravimetric analysis, and single X-ray crystallography.
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U2 - 10.1021/ic0506005
DO - 10.1021/ic0506005
M3 - Article
C2 - 16060627
AN - SCOPUS:23844496393
SN - 0020-1669
VL - 44
SP - 5753
EP - 5760
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 16
ER -