New way to formation of perthiocarbonate ligand - Synthesis and crystal structures of [Me4N](n)[Cu(CS4)] (n)(I) and [Me4N](4)[Cu-4(CS4)(4)](II)

Citation
Kl. Tang et al., New way to formation of perthiocarbonate ligand - Synthesis and crystal structures of [Me4N](n)[Cu(CS4)] (n)(I) and [Me4N](4)[Cu-4(CS4)(4)](II), CHEM J CH U, 22(5), 2001, pp. 717-721
Citations number
17
Language
CHINESE
art.tipo
Article
Categorie Soggetti
Chemistry
Journal title
CHEMICAL JOURNAL OF CHINESE UNIVERSITIES-CHINESE
ISSN journal
0251-0790 → ACNP
Volume
22
Issue
5
Year of publication
2001
Pages
717 - 721
Database
ISI
SICI code
0251-0790(200105)22:5<717:NWTFOP>2.0.ZU;2-8
Abstract
The solutions of tetranuclear copper cluster anionic complexes [Me4N](2) [C u-4 (SePh)(6)] or [Me4N](2)[Cu-4(SPh)(6)] in DMF or CH3CN reacted with CS2 in the presence of a small amount of S. From the resulting solutions brown- black block-shaped crystals I or brown-red block-shaped crystals II were fo rmed, respectively. Crystal data: (I) orthorhombic, space group Pbca, a = 1 .138 5(4) nm, b = 1.668 3(4) nm, c = 1.092 1(2) nm, V = 2.074 2(9) nm(3). m u = 2.846 mm(-1), F(000) = 1 136 e, D-e = 1.777 g/cm(3), for Z = 8, R = 0.0 54 4 for 1 821 observed reflections; (II) tetragonal, space group P (4) ove r bar2(1)c, a = 1.395 2(2) nm, b = 1.395 2(2) nm, c = 1. 135 0(2) nm, V = 2 .209 4(6) nm(3). mu = 2.677,mm(-1), F(000) = 1 136e, D-c = 1.671 g/cm(3), f or Z = 8, R = 0.064 5 for 1 114 observed reflections. The X-ray crystal str ucture determination indicated that the molecule of the complex I consists of a polymeric anion [Cu-2 (CS4)(2)](n)(2-) and cations-[Me4N](+). In the p olymeric anion, the repeated unit is a dinuclear copper complex [CU2(CS4)(2 )](2-) which links to four surrounding aggregations through sulfur bridges to form a two-dimensional layer structure. The cations [Me4N)(+) locate bet ween the layers. The molecule of complex II consists of a tetranuclear copp er cluster anion with four perthiocarbonate ligands [Cu-4(CS4)(4)](4-) and four cations [Me4N](+). The four copper atoms form a tetrahedron. One of th e sulfur atoms in each CS42- ligand forms the sulfur bridge with two Cu ato ms while the other is coordinated to only one copper.