871810-44-5Relevant academic research and scientific papers
Synchrotron powder diffraction in a systematic study of 4′-[2-(tosylamino)benzylideneamino]-2,3-benzo-15-crown-5 complexes
Dorokhov, Andrey V.,Chernyshov, Dmitrii Yu.,Burlov, Anatolii S.,Garnovskii, Alexandr D.,Ivanova, Irina S.,Pyatova, Elena N.,Tsivadze, Aslan Yu.,Aslanov, Leonid A.,Chernyshev, Vladimir V.
, p. 402 - 410 (2007)
The crystal structures of two compounds, CuL 2 and LiNCS·HL [HL = 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 CuL 2 the four N atoms of two bidentate L ligands coordinate the CuII ion in a distorted tetrahedral geometry with Cu - N distances of 1.98 (5)-2.05 (5) A, while two O atoms from two sulfoxide groups complete the distorted octahedral Cu coordination [Cu - O 2.64 (4), 2.74 (4) A]. In LiNCS·HL, lithium is coordinated by all five ether O atoms with Li - O distances of 2.03 (3)-2.50 (3) A and an N atom from the thiocyanate moiety [Li - N 1.98 (3) A] in a distorted pentagonal pyramidal geometry. Preliminary potentiometric selectivity measurements for ion-selective electrodes (ISEs) based on CuL 2 and ZnL 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 CuL 2, LiNCS·HL, ZnL 2 and HL 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 CuL 2 and ZnL 2 results in different potentiometric selectivities of ISEs based on these compounds. International Union of Crystallography 2007.
