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

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.