In:
Acta Crystallographica Section B Structural Science, International Union of Crystallography (IUCr), Vol. 63, No. 3 ( 2007-06-01), p. 402-410
Abstract:
The crystal structures of two compounds, Cu L 2 and LiNCS·H L [H L = 4′-[2-(tosylamino)benzylideneamino]-2,3-benzo-15-crown-5] , have been determined from synchrotron powder diffraction data. Both compounds crystallize in the monoclinic space group P2 1 / c and with one molecule in the asymmetric unit. In Cu L 2 the four N atoms of two bidentate L ligands coordinate the Cu II ion in a distorted tetrahedral geometry with Cu—N distances of 1.98 (5)–2.05 (5) Å, while two O atoms from two sulfoxide groups complete the distorted octahedral Cu coordination [Cu—O 2.64 (4), 2.74 (4) Å]. In LiNCS·H L , lithium is coordinated by all five ether O atoms with Li—O distances of 2.03 (3)–2.50 (3) Å and an N atom from the thiocyanate moiety [Li—N 1.98 (3) Å] in a distorted pentagonal pyramidal geometry. Preliminary potentiometric selectivity measurements for ion-selective electrodes (ISEs) based on Cu L 2 and Zn L 2 demonstrated significant differences in their selectivity. In order to find a possible reason for this, theoretical calculations at the DFT (B3LYP) level were performed. These calculations used the crystal structures of Cu L 2 , LiNCS·H L , Zn L 2 and H L as input geometries for the minimum energy optimization in vacuo . The results indicate that in ML 2 complexes ( M = Cu, Zn) the electronic structure of the metal ion determines the spatial orientation of benzo-15-crown-5 macrocycles, and their different orientation in Cu L 2 and Zn L 2 results in different potentiometric selectivities of ISEs based on these compounds.
Type of Medium:
Online Resource
ISSN:
0108-7681
DOI:
10.1107/S0108768107003898
DOI:
10.1107/S0108768107003898/kd5008sup1.cif
DOI:
10.1107/S0108768107003898/kd5008LiNCSsup2.rtv
DOI:
10.1107/S0108768107003898/kd5008CuL2sup3.rtv
DOI:
10.1107/S0108768107003898/kd5008sup4.pdf
Language:
Unknown
Publisher:
International Union of Crystallography (IUCr)
Publication Date:
2007
detail.hit.zdb_id:
2020841-8
SSG:
13
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