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Two Examples of Novel and Unusual Double‐Layered, Two‐Dimensional Cu II Compounds with Bridging 1,3‐Bis(1,2,4‐triazol‐1‐yl)propane
Author(s) -
van Albada Gerard A.,
Guijt Reinier C.,
Haasnoot Jaap G.,
Lutz Martin,
Spek Anthony L.,
Reedijk Jan
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(200001)2000:1<121::aid-ejic121>3.0.co;2-d
Subject(s) - chemistry , acetonitrile , crystallography , octahedron , propane , molecule , ion , copper , electron paramagnetic resonance , crystal structure , stereochemistry , solvent , organic chemistry , nuclear magnetic resonance , physics
The synthesis and characterisation of two new polymeric Cu II complexes is described, i.e. {[Cu(btp) 2 (CH 3 CN)(H 2 O)](CF 3 SO 3 ) 2 } n ( 1 ) and {[Cu(btp) 2 (CH 3 CN) 2 ](ClO 4 ) 2 } n ( 2 ), in which btp = [1,3‐bis(1,2,4‐triazol‐1‐yl)propane]. Compound 1 crystallizes in space group P 2 1 / c with a = 11.9337(15) Å, b = 20.108(6) Å, c = 12.748(6) Å, β = 92.247(14)°, and Z = 4. Compound 2 crystallizes in space group Pna 2 1 with a = 18.770(8) Å, b = 12.648(8) Å, and c = 12.019(8) Å. The structures refined to R 1 values of 0.0683 for 1 and 0.0846 for 2 . In both structures the Cu II ions are linked by the bridging ligands, resulting in two‐dimensional networks. Two such curved layers are arranged on top of each other with center‐to‐center of layer distances of 2.12 Å in 1 and 1.98 Å in 2 . Such double layers are separated from each other by 10.05 Å in 1 and 9.385 Å in 2 . The space between the double layers is occupied with interstitial anions. No significant interaction between Cu II ions is observed by EPR and magnetic susceptibility measurements. The compounds form a new class of a lattice engineered system held together by the Cu II ions. – The coordination geometry of the copper ions is distorted octahedral, with the equatorial plane formed by the N4 nitrogens of the four triazole groups and the axial sites occupied by solvent molecules; acetonitrile and water in structure 1 and two acetonitrile molecules in structure 2 . The two structures are related by a group–subgroup relationship, which appears to be the first such case in supramolecular chemistry. – The Cu–N vibrations in the FIR region are found at 274 cm –1 for 1 , and at 276 cm –1 for 2 . The ligand‐field maxima are observed at about 16·10 3 cm –1 , with a shoulder at about 12·10 3 cm –1 . The ν CN stretching vibrations of the acetonitrile molecules are found at 2303 and 2261 cm –1 for 1 , and at 2313, 2294, 2278, and 2260 cm –1 for 2 .