Crystal structures of three anionic lanthanide-aluminium [3.3.1] metallacryptate complexes

Abstract

The three isomorphous [3.3.1] metallacryptate complexes bis­(pyridinium) di­aqua­dipyridine­hexa­kis­[μ 3 -salicyl­hydroximato(3-)]bis­[μ 2 -salicyl­hydroxim­ato(1-)]hexa­aluminiumgadolinium-pyridine-water (1/7.396/1), (C 5 H 6 N) 2 [GdAl 6 (C 7 H 6 NO 3) 2 (C 7 H 4 NO 3) 7 (C 5 H 5 N) 1.855 (H 2 O) 2 ]·7.396C 5 H 5 N·H 2 O or [Hpy] 2 [GdAl 6 (H 2 shi) 2 (shi) 7 (py) 1.855 (H 2 O) 2 ]·7.396py·H 2 O, 1, bis­(pyridinium) di­aqua­dipyridine­hexa­kis­[μ 3 -salicyl­hydroximato(3-)]bis­[μ 2 -salicyl­hydroxim­ato(1-)]hexa­aluminiumdysprosium-pyridine-water (1/7.429/1), (C 5 H 6 N) 2 [DyAl 6 (C 7 H 6 NO 3) 2 (C 7 H 4 NO 3) 7 (C 5 H 5 N) 1.855 (H 2 O) 2 ]·7.429C 5 H 5 N·H 2 O or [Hpy] 2 [DyAl 6 (H 2 shi) 2 (shi) 7 (py) 1.891 (H 2 O) 2 ]·7.429py·H 2 O, 2, and bis­(pyrid­in­ium) di­aqua­dipyridine­hexa­kis­[μ 3 -salicyl­hydroximato(3-)]bis­[μ 2 -salicyl­hydrox­imato(1-)]hexa­aluminiumytterbium-pyridine-water (1/7.386/1), (C 5 H 6 N) 2 [YbAl 6 (C 7 H 6 NO 3) 2 (C 7 H 4 NO 3) 7 (C 5 H 5 N) 1.855 (H 2 O) 2 ]·7.429C 5 H 5 N·H 2 O or [Hpy] 2 [YbAl 6 (H 2 shi) 2 (shi) 7 (py) 1.818 (H 2 O) 2 ]·7.386py·H 2 O, 3, where Hpy + is pyridinium, shi 3- is salicyl­hydroximate, and py is pyridine, consist of an aluminium-based metallacryptand that captures an Ln III ion in the central cavity. The metallacryptand portions are comprised of an Al - N - O repeat unit; thus, they can be considered three-dimensional metallacrowns. The encapsulated Ln III ions are nine-coordinate with a spherical capped-square-anti­prism geometry, while the six Al III ions are all octa­hedral. Four of the Al III ions are chiral centers with 2 Δ and 2 Λ stereoconfigurations. The remaining two Al III ions have trans chelate rings from two different shi 3- ligands. For 1-3, a section of the main mol­ecule is disordered induced by the presence or absence of a pyridine ligand coordinated to one of the Al III ions. In the absence of the pyridine moiety, an H 2 shi - ligand moves into the space otherwise occupied by the pyridine and the phenol oxygen atom coordinates to the Al III ion. The movement of the H 2 shi - ligand induces movement for the Ln III ion, for another Al III ion that also binds the same H 2 shi - ligand, and for one of the shi 3- ligands coordinated to the latter Al III ion. For 1-3 the occupancy ratio of the metallacryptand portions refined to 0.8550 (13):0.1450 (13), to 0.8909 (13):0.1091 (13), and to 0.8181 (14):0.1819 (14), respectively.