Journal of Mineralogical and Petrological Sciences
Online ISSN : 1349-3825
Print ISSN : 1345-6296
ISSN-L : 1345-6296
Crystal structure refinement and crystal chemistry of parasymplesite and vivianite
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2021 Volume 116 Issue 4 Pages 183-192


Parasymplesite and vivianite specimens were obtained from Kiura Mine, Ohita, Japan and Tomigaoka, Nara, Japan, respectively. Empirical chemical formulas of the specimens determined by energy–dispersive X–ray spectroscopy on the scanning electron microscopy were Fe3(AsO4)2·8H2O, and (Fe0.93Mn0.06Mg0.01)3(PO4)2·8H2O, respectively. The crystal structures of parasymplesite and vivianite determined by single–crystal X–ray diffraction method were monoclinic, space group C2/m, with unit–cell parameters: a = 10.3519(10), b = 13.6009(13), c = 4.7998(4) Å, β = 104.816(2)°, V = 653.32(11) Å3 (Z = 4), and monoclinic, space group C2/m, with unit–cell parameters: a = 10.1518(6), b = 13.4327(7), c = 4.7005(3) Å, β = 104.692(2)°, V = 620.03(6) Å3 (Z = 4), respectively. The crystal structure of parasymplesite solved with the ideal chemical formula was refined to the R1 value of 0.0301 (wR2 = 0.0788) for 722 independent reflections with |Fo| > 4σ(|Fo|), whereas that of vivianite was refined to the R1 value of 0.0272 (wR2 = 0.0832) for 664 independent reflections. The hydrogen atom positions determined by the difference Fourier method coincided with the positions where residual electron density peaks appeared. In the edge–sharing Fe2O6(H2O)4 double octahedra in parasymplesite and vivianite, the bond distance of Fe2–O5, where O5 is the oxygen atom of the H2O molecule, is shorter than that of Fe2–O2. In each arsenate and phosphate phase, only the M2–O2 bond distance shows an increase trend with the increase in the average ionic radii of the M2 site, but the M2–O3 bond distance never shows a clear average M2 ionic radius dependence. In vivianite group minerals, a distortion at the isolated M1O2(H2O)4 octahedra increases as a function of the average M1 ionic radius. The respective complex sheets consisting of the TO4 tetrahedra, isolated M1 octahedra, and edge–sharing M2 double octahedra are connected only by the hydrogen bond O5–H52•••O4. In the arsenate phases, the donor–acceptor distance between O5 and O4 exhibits an increase trend as increase of the average M ionic radius, but in the phosphate phases, there is no clear correlation between donor–acceptor distances and the average M ionic radius.

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