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A new mixed-valence lead(II) mangan-ese(II/III) phosphate(V): PbMn(II) 2Mn(III)(PO4)3.

ABSTRACT: The title compound, lead trimanganese tris(orthophosphate), has been synthesized by hydro-thermal methods. In this structure, only two O atoms are in general positions and all others atoms are in the special positions of the Imma space group. Indeed, the atoms in the Wyckoff positions are namely: Pb1 and P1 on 4e (mm2); Mn1 on 4b (2/m); Mn2 and P2 on 8g (2); O1 on 8h (m); O2 on 8i (m). The crystal structure can be viewed as a three-dimensional network of corner- and edge-sharing PO4 tetra-hedra and MnO6 octa-hedra, building two types of chains running along the b axis. The first is an infinite linear chain, formed by alternating Mn(III)O6 octa-hedra and PO4 tetra-hedra which share one vertex. The second chain is built up from two adjacent edge-sharing octa-hedra (Mn(II) 2O10 dimers) whose ends are linked to two PO4 tetra-hedra by a common edge. These chains are linked together by common vertices of polyhedra in such a way as to form porous layers parallel to (001). These sheets are bonded by the first linear chains, leading to the appearance of two types of tunnels, one propagating along the a axis and the other along b. The Pb(II) ions are located within the inter-sections of the tunnels with eight neighbouring O atoms in form of a trigonal prism that is capped by two O atoms on one side. The three-dimensional framework of this structure is compared with similar phosphates such as Ag2Co3(HPO4)(PO4)2 and Ag2Ni3(HPO4)(PO4)2.

SUBMITTER: Alhakmi G

PROVIDER: S-EPMC3772398 | biostudies-literature | 2013

REPOSITORIES: biostudies-literature

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A new mixed-valence lead(II) mangan-ese(II/III) phosphate(V): PbMn(II) 2Mn(III)(PO4)3.

Alhakmi Ghaleb G Assani Abderrazzak A Saadi Mohamed M El Ammari Lahcen L

Acta crystallographica. Section E, Structure reports online 20130622 Pt 7

The title compound, lead trimanganese tris(orthophosphate), has been synthesized by hydro-thermal methods. In this structure, only two O atoms are in general positions and all others atoms are in the special positions of the Imma space group. Indeed, the atoms in the Wyckoff positions are namely: Pb1 and P1 on 4e (mm2); Mn1 on 4b (2/m); Mn2 and P2 on 8g (2); O1 on 8h (m); O2 on 8i (m). The crystal structure can be viewed as a three-dimensional network of corner- and edge-sharing PO4 tetra-hedra ...[more]

PMID: 24046541

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Project description:The reaction of 2,6-diformyl-4-methylphenol (DFMF) with 1-amino-2-propanol (AP) and tris(hydroxymethyl)aminomethane (THMAM) was investigated in the presence of Cobalt(II) salts, (X = ClO4-, CH3CO2-, Cl-, NO3-), sodium azide (NaN3), and triethylamine (TEA). In one pot, the variation in Cobalt(II) salt results in the self-assembly of dinuclear, tetranuclear, and H-bonding-directed polynuclear coordination complexes of Cobalt(III), Cobalt(II), and mixed-valence CoIICoIII: [Co2III(H2L-1)2(AP-1)(N3)](ClO4)2 (1), [Co4(H2L-1)2(µ3-1,1,1-N3)2(µ-1,1-N3)2Cl2(CH3OH)2]·4CH3OH (2), [Co2IICo2III(HL-2)2(µ-CH3CO2)2(µ3-OH)2](NO3)2·2CH3CH2OH (3), and [Co2IICo2III (H2L12-)2(THMAM-1)2](NO3)4 (4). In 1, two cobalt(III) ions are connected via three single atom bridges; two from deprotonated ethanolic oxygen atoms in the side arms of the ligands and one from the1-amino-2-propanol moiety forming a dinuclear unit with a very short (2.5430(11) Å) Co-Co intermetallic separation with a coordination number of 7, a rare feature for cobalt(III). In 2, two cobalt(II) ions in a dinuclear unit are bridged through phenoxide O and μ3-1,1,1-N3 azido bridges, and the two dinuclear units are interconnected by two μ-1,1-N3 and two μ3-1,1,1-N3 azido bridges generating tetranuclear cationic [Co4(H2L-1)2(µ3-1,1,1-N3)2(µ-1,1-N3)2Cl2(CH3OH)2]2+ units with an incomplete double cubane core, which grow into polynuclear 1D-single chains along the a-axis through H-bonding. In 3, HL2- holds mixed-valent Co(II)/Co(III) ions in a dinuclear unit bridged via phenoxide O, μ-1,3-CH3CO2-, and μ3-OH- bridges, and the dinuclear units are interconnected through two deprotonated ethanolic O in the side arms of the ligands and two μ3-OH- bridges generating cationic tetranuclear [Co2IICo2III(HL-2)2(µ-CH3CO2)2(µ3-OH)2]2+ units with an incomplete double cubane core. In 4, H2L1-2 holds mixed-valent Co(II)/Co(III) ions in dinuclear units which dimerize through two ethanolic O (μ-RO-) in the side arms of the ligands and two ethanolic O (μ3-RO-) of THMAM bridges producing centrosymmetric cationic tetranuclear [Co2IICo2III (H2L1-2)2(THMAM-1)2]4+ units which grow into 2D-sheets along the bc-axis through a network of H-bonding. Bulk magnetization measurements on 2 demonstrate that the magnetic interactions are completely dominated by an overall ferromagnetic coupling occurring between Co(II) ions.

Dataset Information

A new mixed-valence lead(II) mangan-ese(II/III) phosphate(V): PbMn(II) 2Mn(III)(PO4)3.

Publications

A new mixed-valence lead(II) mangan-ese(II/III) phosphate(V): PbMn(II) 2Mn(III)(PO4)3.

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