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The crystal structure of Ca5(PO4)2SiO4 (Silico-Carnotite)

Die Kristallstruktur vonCa 5(PO 4)2 SiO 4 (Silicocarnotit)

Summary

The crystal structure of Ca5(PO4)2SiO4 (silico-carnotite) has been determined from 3358 x-ray diffraction data collected by a counter method and has been refined toR w =0.038,R=0.045, in space group Pnma. The unit cell parameters area=6.737 (1) Å,b=15.508 (2) Å andc=10.132 (1) Å at 24°C;Z=4. The observed density is 3.06 and the calculated density is 3.03 g · cm−3. The crystal contains about 2.5% V2O5 as an impurity. The bond lengths within the tetrahedral anions suggest that substitution or disorder of PO4 3−, SiO4 4− and possibly VO4 3− occurs among the anion sites. The structure has some relationship to that of Ca5(PO4)3OH, the predominant inorganic phase in the human body, but suggests that the Ca5(PO4)3OH type structure may not be stable without some of the OH positions being filled. Ca5(PO4)2SiO4 is more closely related to K3Na(SO4)2 (glaserite) if it is considered that there are systematic cation vacancies in Ca5(PO4)2SiO4.

This type of structure is consistent with the view that cation vacancies in the glaserite-type structure account for solid solutions between Ca2SiO4 and Ca3(PO4)2 and between Ca3(PO4)2 and CaNaPO4.

Zusammenfassung

Die Kristallstruktur von Ca5(PO4)2SiO4 (Silicocarnotit) wurde aus 3358 Röntgendiffraktometer-Daten bestimmt und in Raumgruppe Pnma aufR w =0,038,R=0,045 verfeinert. Die Gitterkonstanten (bei 24° C) sind:a=6,737 (1) Å,b=15,508 (2) Å undc=10,132 (1) Å,Z=4; Dobs.=3,06 g · cm−3, Dexp.=3,03 g · cm−3. Der Kristall enthält etwa 2,5% V2O5 als Verunreinigung. Die Bindungslängen in den tetraedrischen Anionen legen nahe, daß unter den Anionenplätzen gegenseitige Vertretung oder Unordnung von PO4 3−, SiO4 4− und möglicherweise VO4 3− auftritt. Die Struktur zeigt einige Verwandtschaft zu der von Ca5(PO4)3OH, der wichtigsten anorganischen Substanz im menschlichen Körper, weist aber darauf hin, daß eine Struktur vom Ca5(PO4)3OH-Typ ohne Besetzung eines Teiles der OH-Position nicht stabil ist. Ca5(PO4)2SiO4 zeigt engere Beziehungen zu K3Na(SO4)2 (Glaserit), wenn man berücksichtigt, daß in Ca5(PO4)3SiO4 systematische Kationen-Leerstellen sind. Dieser Strukturtyp ist mit der

Auffassung in Übereinstimmung, daß Kationenleerstellen für die festen Lösungen zwischen Ca2SiO4 und Ca3(PO4)2 und zwischen Ca3(PO4)2 und CaNaPO4 verantwortlich sind.

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Dickens, B., Brown, W.E. The crystal structure of Ca5(PO4)2SiO4 (Silico-Carnotite). TMPM Tschermaks Petr. Mitt. 16, 1–27 (1971). https://doi.org/10.1007/BF01099075

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Keywords

  • Geochemistry
  • V2O5
  • Unit Cell Parameter
  • Counter Method
  • Cation Vacancy