Incorporation of μ3-CO3 into an MnIII/MnIV Mn12 cluster: {[(cyclam)MnIV(μ-O)2MnIII(H2O)(μ-OH)]6(μ3-CO3)2}Cl8·24H2O

The centrosymmetric title cluster, hexa­aquadi-μ3-carbonato-hexa­cyclamhexa-μ2-hydroxido-dodeca-μ2-oxido-hexa­mang­an­ese(IV)hexa­manganese(III) octa­chloride tetra­cosa­hydrate, [Mn12(CO3)2O12(OH)6(C10H24N4)6(H2O)6]Cl8·24H2O, has two μ3-CO3 groups that not only bridge octahedrally coordinated MnIII ions but also act as acceptors to two different kinds of hydrogen bonds. The carbonate anion is planar within experimental error and has an average C—O distance of 1.294 (4) Å. The crystal packing is stabilized by O—H⋯Cl, O—H⋯O, N—H⋯Cl and N—H⋯O hydrogen bonds. Two of the four independent chloride ions are disordered over five positions, and eight of the 12 independent water mol­ecules are disordered over 21 positions

Carbonate-Templated Self-Assembly of an Alkylthiolate-Bridged Cadmium Macrocycle

In the presence of Cd(ClO4)2 and a base, a new mixed N,S-donor alkylthiolate ligand supported both carbonate formation from atmospheric CO2 and the self-assembly of a novel bicapped puckered (CdS)6 molecular wheel. The remarkable stability of the complex was demonstrated by slow intermolecular ligand exchange on the 2J(HH) and J(111/113Cd1H) time scales at elevated temperature. Both CO2 and the base were required to convert amorphous “CdLClO4” precipitated in the absence of air to the carbonate complex. The complex shares structural features with the ζ-carbonic anhydrase class associating cadmium(II) with the biogeochemical cycling of carbon and is the first structurally characterized carbonate complex of any metal involving an alkylthiolate ligand

Incorporation of μ(3)-CO(3) into an Mn/Mn Mn(12) cluster: {[(cyclam)Mn(μ-O)(2)Mn(H(2)O)(μ-OH)](6)(μ(3)-CO(3))(2)}Cl(8)·24H(2)O.

The centrosymmetric title cluster, hexa-aquadi-μ(3)-carbonato-hexa-cyclamhexa-μ(2)-hydroxido-dodeca-μ(2)-oxido-hexa-mang-an-ese(IV)hexa-manganese(III) octa-chloride tetra-cosa-hydrate, [Mn(12)(CO(3))(2)O(12)(OH)(6)(C(10)H(24)N(4))(6)(H(2)O)(6)]Cl(8)·24H(2)O, has two μ(3)-CO(3) groups that not only bridge octahedrally coordinated Mn(III) ions but also act as acceptors to two different kinds of hydrogen bonds. The carbonate anion is planar within experimental error and has an average C-O distance of 1.294 (4) Å. The crystal packing is stabilized by O-H⋯Cl, O-H⋯O, N-H⋯Cl and N-H⋯O hydrogen bonds. Two of the four independent chloride ions are disordered over five positions, and eight of the 12 independent water mol-ecules are disordered over 21 positions

Incorporation of μ(3)-CO(3) into an Mn/Mn Mn(12) cluster: {[(cyclam)Mn(μ-O)(2)Mn(H(2)O)(μ-OH)](6)(μ(3)-CO(3))(2)}Cl(8)·24H(2)O.

The centrosymmetric title cluster, hexa-aquadi-μ(3)-carbonato-hexa-cyclamhexa-μ(2)-hydroxido-dodeca-μ(2)-oxido-hexa-mang-an-ese(IV)hexa-manganese(III) octa-chloride tetra-cosa-hydrate, [Mn(12)(CO(3))(2)O(12)(OH)(6)(C(10)H(24)N(4))(6)(H(2)O)(6)]Cl(8)·24H(2)O, has two μ(3)-CO(3) groups that not only bridge octahedrally coordinated Mn(III) ions but also act as acceptors to two different kinds of hydrogen bonds. The carbonate anion is planar within experimental error and has an average C-O distance of 1.294 (4) Å. The crystal packing is stabilized by O-H⋯Cl, O-H⋯O, N-H⋯Cl and N-H⋯O hydrogen bonds. Two of the four independent chloride ions are disordered over five positions, and eight of the 12 independent water mol-ecules are disordered over 21 positions