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Inter-calated brucite-type layered cobalt(II) hydroxy-sulfate.

ABSTRACT: In an attempt to synthesize new cobalt(II) sulfate framework structures using 1,4-diaza-bicyclo-[2.2.2]octane as a template, crystals of poly[0.35-[hexa-aqua-cobalt(II)] [tri-?-hydroxido-?-sulfato-dicobalt(II)]], {[Co(H(2)O)(6)](0.35)[Co(2)(OH)(3)(SO(4))]}(n), were obtained as a mixture with [Co(H(2)O)(6)]SO(4) crystals. The crystal structure can be described as being constructed from discrete brucite-type [Co(4)(OH)(6)(SO(4))(2)] layers, each of which is built up from edge-shared [Co(OH)(6)] and [Co(OH)(4)(OSO(3))(2)] octa-hedra, with partial inter-calation by [Co(H(2)O)(6)](2+) ions. The absence of ca 30% of the [Co(H(2)O)(6)](2+) cations indicates partial oxidation of cobalt(II) to cobalt(III) within the layer.

SUBMITTER: Yotnoi B

PROVIDER: S-EPMC2969244 | biostudies-literature | 2009 Jun

REPOSITORIES: biostudies-literature

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Inter-calated brucite-type layered cobalt(II) hydroxy-sulfate.

Yotnoi Bunlawee B Luachan Sanchai S Prior Timothy J TJ Rujiwatra Apinpus A

Acta crystallographica. Section E, Structure reports online 20090620 Pt 7

In an attempt to synthesize new cobalt(II) sulfate framework structures using 1,4-diaza-bicyclo-[2.2.2]octane as a template, crystals of poly[0.35-[hexa-aqua-cobalt(II)] [tri-μ-hydroxido-μ-sulfato-dicobalt(II)]], {[Co(H(2)O)(6)](0.35)[Co(2)(OH)(3)(SO(4))]}(n), were obtained as a mixture with [Co(H(2)O)(6)]SO(4) crystals. The crystal structure can be described as being constructed from discrete brucite-type [Co(4)(OH)(6)(SO(4))(2)] layers, each of which is built up from edge-shared [Co(OH)(6)] an ...[more]

PMID: 21582646

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Project description:Ultramafic rocks undergo successive stages of hydration and oxidation during water/rock interaction, giving rise to secondary minerals such as brucite, serpentine, magnetite and the production of H2(g). Ferroan brucite (MgxFe(1-x)2+(OH)2) often forms under low water/rock ratios early during the 'serpentinization' process. The formation of ferroan brucite sequesters Fe(II) and suppresses the production of H2, thereby limiting the flux of reductants suitable for sustaining microbial metabolism. Yet ferroan brucite is a relatively soluble mineral 'reservoir' for reactive Fe(II). Brucite is often metastable and can be lost at later stages of peridotite hydration when there is a significant increase in the water/rock ratio or the activity of SiO2 or CO2. The Fe(OH)2 component of brucite has the thermodynamic potential to reduce most aqueous oxidants. Therefore, ferroan brucite may reduce water and/or dissolved carbon, nitrogen and sulfur species, while the Fe(II) is converted into more stable secondary minerals such as Fe(II/III)-oxides and hydroxides (e.g. green-rust, magnetite, iowaite and pyroaurite) and ferric serpentine. The reactivity of ferroan brucite, and the associated rate of Fe solubilization and oxidation in subsurface fluids, could be a key regulator on the rate of electron transfer from serpentinites to the rock-hosted biosphere. Aqueous alteration of ferroan brucite may significantly modulate the H2 activity in fluids circulating within partially serpentinized rocks, and buffer H2 as it is lost by advection or in situ consumption by a hydrogenotrophic microbial community. Moreover, there may be microbial organisms that specifically colonize and use ferroan brucite as an electron donor for their metabolism. The energy fluxes sustained by localized brucite oxidation may often be sufficiently large to sustain abundant microbial communities; water/rock reaction zones where brucite is consumed could serve as environments to search for extant or fossil serpentinite-hosted life. This article is part of a discussion meeting issue 'Serpentinite in the Earth System'.

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Inter-calated brucite-type layered cobalt(II) hydroxy-sulfate.

Publications

Inter-calated brucite-type layered cobalt(II) hydroxy-sulfate.

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