Zi-Yi Du

Octanuclear Aluminum(III) and Iron(III) Phosphonate Cages Encapsulating Two NaI Ions

Hydrothermal reactions of aluminum(III) nitrate or iron(III) nitrate with N,N-dimethylaminomethane-1,1-diphosphonic acid (H(4)L) and sodium hydroxide lead to two novel isostructural octanuclear metal phosphonate cages encapsulating two Na(I) ions, namely, [Al(8)Na(2)(HL)(2)(H(2)L)(10)(H(2)O)(6)] x 20 H(2)O (1) and [Fe(8)Na(2)(HL)(2)(H(2)L)(10)(H(2)O)(6)] x 22 H(2)O (2). The molecular structure of 1 can be viewed as a three-in-one cluster, in which a central zeolite D6R SBU lookalike aluminophosphonate cage is capped by two symmetry-related aluminophosphonate tetrahedral cages above and below and such a tetrahedral cage, being composed of four zeolite S6R SBU lookalike aluminophosphonate rings, further hexadentately traps one Na(+) ion in its cavity.

Hydrogen-bonded layers directed by the [3-O3S-C6H4-PO3H]2- dianion: catena-poly[[silver(I)-mu-4,4'-bipyridine-kappa2N:N'] 3-[hydroxy(oxido)phosphinoyl]benzenesulfonate trihydrate] and catena-poly[[[tetraaquacobalt(II)]-mu-4,4'-bipyridine-kappa2N:N'] 3-[hydroxy(oxido)phosphinoyl]benzenesulfonate].

Both title compounds, {[Ag(2)(C(10)H(8)N(2))(2)](C(6)H(5)O(6)PS).3H(2)O}(n), (I), and {[Co(C(10)H(8)N(2))(2)(H(2)O)(4)](C(6)H(5)O(6)PS)}(n), (II), respectively, contain similar novel symmetric dimeric [O(3)S-C(6)H(4)-PO(3)H](2-) anions formed via two shared (O...H...O) H atoms on twofold positions between two -PO(3)H(-) groups. The two-coordinate Ag(I) structure features one-dimensional polymeric chains of {[Ag(4,4-bipy)](2)(2+)}(n) (4,4-bipy is 4,4-bipyridine), weakly linked by pi-pi interactions, separated by the anionic dimers which are stabilized into layers by hydrogen bonding to three water molecules. In (II), a twofold crystallographic axis runs through the one-dimensional {[Co(4,4-bipy)(H(2)O)(4)](2+)}(n) chains containing six-coordinate Co(II); three-dimensional packing is provided by hydrogen bonding using all sulfonate and -PO(3)H(-) O atoms as acceptors and the Co-bound water H atoms as donors. In this latter case, the benzenesulfonate aromatic rings are also constrained to a mirror plane. This report illustrates how a previously unreported dianion can affect the crystallization of polymeric metal complex cations.

Poly[aqua(μ2‐4,4′‐bipyridyl‐κ2N:N′)(μ2‐3‐phosphonatobenzenesulfonato‐κ2O:O′)copper(II)]

The title polymer, [Cu(C6H5O6PS)(C10H8N2)(H2O)]n, was synthesized by a hydroxadthermal method. The CuII ion is five-coordinated by one phosphoxadnate O atom, one sulfonate O atom, two N atoms of the bipyridyl ligand and one water molxadecule. The coordination geometry around the metal centre can be described as slightly distorted square-pyramidal. The CuII ions are connected by bidentate bridging phosphoxadnato-benzenexadsulfonate ligands, forming one-dimensional helical chains along [010], which are further bridged by bidentate 4,4′-bipyridyl ligands, generating a two-dimensional layered crystal structure. The layered structure features an eight-membered ring including four CuII ions, two [O3S–C6H4–PO3H]2− anions and two 4,4′-bipyridyl ligands. Hydrogen bonds involving aqua ligands, phosphoxadnate O and sulfonate O atoms are observed between the layers,