Premium
The Unexpected Versatility of P 4 S 3 as a Building Block in Polymeric Copper Halide Networks: 2,3‐P, 1,2,3‐P and all‐P Coordination
Author(s) -
Biegerl Andreas,
Brunner Eike,
Gröger Christian,
Scheer Manfred,
Wachter Joachim,
Zabel Manfred
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200700761
Subject(s) - crystallography , copper , chemistry , halide , molecule , crystal structure , ligand (biochemistry) , coordination polymer , inorganic chemistry , biochemistry , receptor , organic chemistry
Layering solutions of P 4 S 3 in CH 2 Cl 2 with solutions of CuCl or CuI in CH 3 CN gives the coordination polymers (P 4 S 3 ) 3 (CuCl) 7 ( 1 ), (P 4 S 3 ) 2 (CuCl) 3 ( 2 ), (P 4 S 3 )(CuI) ( 3 ) and (P 4 S 3 )(CuI) 3 ( 4 ), respectively, after slow diffusion. The yellow compounds were characterised by elemental analysis, 31 P magic‐angle spinning (MAS) NMR spectroscopy and single‐crystal X‐ray crystallography. The solid‐state structures demonstrate the unexpected ligand versatility of the P 4 S 3 molecule, which interacts through two, three, or even all of the phosphorus atoms with copper according to the nature of the copper halide. Compound 1 has a three‐dimensional network in which linear and cylindrical infinite CuCl subunits coexist with diatomic CuCl building blocks. For the first time, all four P atoms of the P 4 S 3 cage are involved in coordination with metal atoms. The 3D structure of 2 contains stacks of P 4 S 3 that are interconnected by slightly undulated and planar [CuCl] n ribbons. Compound 3 is a one‐dimensional polymer composed of alternating (CuI) 2 rings and P 4 S 3 bridges. The structure of 4 consists of undulated [CuI] n layers in which the P 4 S 3 cage functions as a bridge within the layer, as well as a spacer between the layers. The 31 P MAS NMR spectra obtained are in good agreement with the solid‐state structures obtained crystallographically. Thus, analytically pure 3 and 4 show singlet peaks that correspond to uncoordinated P and quartets owing to coupling with 63 Cu and 65 Cu, respectively, whereas that of 1 contains quartets according to all‐P coordination. The spectrum of 2 was obtained from a sample that still contained 40 % of 1 .