Crystal structures of the methanol and hexanol adducts of tris(8-quinolinolato)manganese(III)

Abstract

Both the methanol and hexanol adducts of tris(8-quinolinolato)manganese (III) have been shown to be isomorphic. They crystallize in the monoclinic space group P21/n with four molecules in the unit-cell. The cell dimensions of the methanol adduct are a = 10.847(3), b = 13.201(4), c = 17.285(5) A = 97.56(5)~ ; the asymmetric molecular unit being Mn(C9 H6 NO) 3 9 CH3 OH. For the hexanol adduct, a = 11.201(4), b=13.342(4), c= 17.200(5))~, = 97.09(6) ~ , with an asymmetric molecular unit, Mn(CgH 6NO)3 -89The methanol adduct structure was deduced from CuKa intensities visually estimated from Weissenberg films, but refined on data remeasured on a four-circle diffractometer. Data measured with MoKa radiation on a diffractometer was used for the analysis of the hexanol adduct. Both structures were solved by the heavy-atom method and refined by difference and least-squares procedures. An R of 0.079 for the 1536 observed terms of the methanol structure and an R of 0.063 for the 2509 observed terms of the hexanol structure were attained. The complexes are in the meridiona~ conformation, with the manganese atoms coordinated to the bidentate 8-quinolinol ligands in a distorted octahedral configuration. In the methanol structure, two methanol molecules related by the crystallographic center of symmetry lie in a "cage-like" cavity in the crystal structure, whereas in the hexanol structure only one hexanol molecule is so accommodated. The latter is disordered, the crystallographicalty imposed symmetry requiring that it adopts two orientations in the unit-cell.

The role of CH–π interaction in the charge transfer properties in tris(8-hydroxyquinolinato)aluminium(iii)

“…Other molecules surveyed included WUFVAU02 for fac-AlQ 3 , 47 mer-MQ 3 molecules such as GaQ 3 (LOQVUI, 48 -VIYZUY, 40 and ETELAQ 49 ), InQ 3 (WADGUZ 50 and YINRES01 51 ), CoQ 3 (YINRAO01 52 and AJUJIY 53 ), FeQ 3 (MEQDES 54 and RESDOI 55 ), MnQ 3 (MNQOLH10 and MNQOLM10, 56 and ZEMZEW 57 ), VQ 3 (QOFHOI 58 ), CrQ 3 (RADBAA 59 ), RuQ 3 (ZULTAB) 60 RhQ 3 (ZULTEF), 60 and OsQ 3 (ZULSUU). 60 Two six-coordinated metal complexes, bis-(isopropoxido-kO)bis(2-methylquinolin-8-olato-k 2 N,O)titanium(IV) (COLWOQ 61 ) and (2-diphenylphosphino-3,4,5,6-tetrafluorophenyl-C,P)-bis(8-hydroxy-quinolinate-N,O)-rhodium(III) (COWLAB 62 ) were also included.…”

“…Similar CH-p and p-p interacting configurations are also seen in a fac-AlQ 3 crystal, 47 as well as many other six-coordinated molecules containing at least two Q or similar ligands. We have surveyed mer-MQ 3 crystal structures where the central metal ions are Ga(III), 40,48,49 In(III), 50,51 Co(III), 52,53 Fe(III), 54,55 Mn(III), 56,57 V(III), 58 Cr(III, 59 Ru(III), 60 Rh(III), 60 Os(III), 60 and two six-coordinated metal complexes, bis(isopropoxido-kO)bis(2-methylquinolin-8-olato-k 2 N,O)titanium(IV) 61 and (2-diphenylphosphino-3,4,5,6-tetrafluorophenyl-C,P)-bis(8-hydroxyquinolinate-N,O)-rhodium(III). 62 In all cases there exist p-p interacting pairs with CH-p interaction, with the p-p interaction regions shifted towards the pyridyl-pyridyl contact.…”