Affinement de la structure cristalline du cinabre α˗HgS

Auvray, P; Genet, F.

doi:10.3406/bulmi.1973.6816

Cited by 20 publications

(26 citation statements)

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“…The first angle ranges from 89.5° to 95.6° and the second from −86.7 to −101.4° in the optimized Hg 6 S 7 (CH 3 ) 2 model shown in Figure 2a. This conformation is close to that in cinnabar (α-HgS), which has infinite chains throughout its structure with a Hg-S-Hg angle of 104.7° and a dihedral S-S-S-S angle of −98.5°38 (Fig. 2b,c).…”

Section: Resultssupporting

confidence: 60%

“…Once formed, the zigzag -S-(Hg-S) n -Hg-S- chains self-assemble to make the trimer 3[Hg 4 S 5 H 2 ], which is geometrically comparable to three neighboring Hg 4 S 5 units in cinnabar. The coordination around the Hg atoms in α-HgS is “2 + 4”, with two short intra-chain Hg-S bonds 2.37 Å in length and four long inter-chain Hg-S bonds of 3.10–3.29 Å38. Similarly, the cohesion of the HS-(Hg-S) 3 -Hg-SH aggregate is realized by inter-chain Hg-S bonds ranging from 3.15 Å to 3.37 Å.…”

Section: Resultsmentioning

confidence: 99%

“…Hg (dark red) has a natural charge of +1.0 e, sulfide S (yellow) of -1.0 e, thiol S (yellow) of −0.4 e, C (dark gray) of − 0.7 e, and H (light gray) of +0.2 e (not represented). ( b ) Three parallel -S-(Hg-S) n -Hg-S- chains in cinnabar38. ( c ) Cinnabar as an assemblage of replicated chains.…”

Section: Figurementioning

confidence: 99%

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Nucleation of mercury sulfide by dealkylation

Enescu

Nagy

Manceau

2016

Sci Rep

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Metal sulfide minerals are assumed to form naturally at ambient conditions via reaction of a metallic element with (poly)sulfide ions, usually produced by microbes in oxygen-depleted environments. Recently, the formation of mercury sulfide (β-HgS) directly from linear Hg(II)-thiolate complexes (Hg(SR)2) in natural organic matter and in cysteine solutions was demonstrated under aerated conditions. Here, a detailed description of this non-sulfidic reaction is provided by computations at a high level of molecular-orbital theory. The HgS stoichiometry is obtained through the cleavage of the S-C bond in one thiolate, transfer of the resulting alkyl group (R’) to another thiolate, and subsequent elimination of a sulfur atom from the second thiolate as a thioether (RSR’). Repetition of this mechanism leads to the formation of RS-(HgS)n-R chains which may self-assemble in parallel arrays to form cinnabar (α-HgS), or more commonly, quickly condense to four-coordinate metacinnabar (β-HgS). The mechanistic pathway is thermodynamically favorable and its predicted kinetics agrees with experiment. The results provide robust theoretical support for the abiotic natural formation of nanoparticulate HgS under oxic conditions and in the absence of a catalyst, and suggest a new route for the (bio)synthesis of HgS nanoparticles with improved technological properties.

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Section: Resultssupporting

confidence: 60%

Section: Resultsmentioning

confidence: 99%

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Nucleation of mercury sulfide by dealkylation

Enescu

Nagy

Manceau

2016

Sci Rep

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“…~-HgS (cinnabar) Auvray & Genet (1973) and Auvray (1976) concluded that the light rotates in the sense opposite to that of the helix of atoms. We shall show below that this statement was premature, based on a failure to appreciate the distinction between symmetric and non-symmetric structural helices.…”

Section: ~-A1po4 (Berlinite)mentioning

confidence: 99%

On the origin of optical activity in crystal structures

Glazer¹,

Stadnicka²

1986

J Appl Cryst

145

129

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Close examination of published measurements of absolute configuration in inorganic crystals has revealed many mistakes, and only a small number of published correlations between optical rotation and chirality of crystal structure can be trusted. The sense of rotation of light is here traced to the hand of specific helices of atoms, provided that the latter are correctly chosen. Four principles are given for choosing the helices. The crystals described are: low-quartz, ~-A1PO4, ct-HgS, Ca2Sr(CzHsCOO)6, BitzSiO2o, NaC103, NaBrO 3 and ~-LiIO 3. The principles suggest that the published absolute configuration of ~t-LiIO3 must be incorrect {subsequently

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“…[22] Furthermore the ZnϪSϪHgϪSϪZn sequence in 2 is analogous to the 1D polymeric array of mercury and sulfur in cinnabar, the thermodynamically more stable modification of HgS. [23] In cinnabar the HgϪS bond lengths are 2.37 Å and the dihedral angle is 93°. …”

Section: Preparationsmentioning

confidence: 99%