111349-48-5Relevant articles and documents
Heterobimetallic complexes of copper(I) with thiotungstates and thiomolybdates. Synthesis and structural characterization of (PPh4)2[(CuNCS)2WS4] and of polymeric (PPh4)2[(CuNCS)4WS4]
Potvin,Manoli,Sécheresse,Marzak
, p. 4370 - 4374 (2008/10/08)
Reaction of (PPh4)2MS4 (M = Mo, W) with CuCl and KSCN or CuNCS in acetone or acetonitrile affords a new set of mixed metal-sulfur compounds: discrete [(CuNCS)2MS4]2- and polymeric [(CuNCS)4MS4]2- dianions.(PPh4)2[(CuNCS)2WS4] crystallizes in monoclinic space group P21/c with a = 32.89 (2) ?, b = 9.312 (4) ?, c = 17.993 (5) ?, β = 113.11 (4)°, and Z = 4. Least-squares refinement of 328 variables led to a value of the conventional R index (on F) of 0.053 and an Rw value of 0.049 for 3770 reflections with I > 3.0σ(I). The crystal structure of (PPh4)2[(CuNCS)2WS4] (1) reveals the presence of discrete, almost linear trinuclear dianions and involves the coordination of a slightly distorted tetrahedral WS4 moiety to two copper(I) atoms with each trigonal copper(I) atom also participating in Cu-NCS bond lengths of 1.87 (1) and 1.85 (1) ?. This structure contrasts with the polymeric nature of (PPh4)2[(CuNCS)4WS4] (3), which crystallizes in monoclinic space group P21/n with a = 22.641 (9) ?, b = 18.044 (4) ?, c = 14.439 (5) ?, β = 96.22 (4)°, and Z = 4. Least-squares refinement of 400 variables led to a value of the conventional R index (on F) of 0.050 for 6590 reflections with I > 3.0σ(I). The crystal structure determination shows that four edges of the tetrahedral WS4 core are bridged by Cu(I) atoms, giving an aggregate of approximate D2d symmetry with NCS bridges linking different aggregates via two mutually cis pseudotetrahedral coppers to form an infinite zigzag chain running about the 21 axis. One of the remaining two copper atoms adopts a trigonal-planar environment as in 1, while the other cooper atom assumes a geometry intermediate between tetrahedral (short nonbonded distance Cu(3)?S(3) = 3.042 (4) ?) and trigonal planar. These weak interactions between copper and the sulfur atom S(3) of a NCS group lead to a two-dimensional-network polymer parallel to the (101) plane. The electronic spectra of the complexes are dominated by the internal transitions of the MS42- ligand modified by additional CuNCS units. The structural data have been used to interpret vibrational spectroscopic data of the thiocyanate groups.
