NDLI: New Data on the Crystal Structures of Colusites and Arsenosulvanites

Content Provider	Springer Nature Link
Author	Frank Kamenetskaya, O. V. Rozhdestvenskaya, I. V. Yanulova, L. A.
Copyright Year	2002
Abstract	The crystal structures of three minerals (arsenosulvanite, V,As-germanite, and colusite) of the general crystal chemical formula $$Cu_{2 - x}^M V_2^M Cu_{26 - y} $$ (As, Ge, Sn, Sb, V)$_{6}$S$_{32}$, where Cu$^{M}$, V$^{M}$ are cations at interstitial positions, 0.2 ≤ x ≤ 2.0, 2.7 ≥ y ≥ 0, (space group $$P\bar 43n$$ , a = 10.527; 10.600; 10.653 Å; R = 0.066; 0.046; 0.033) have been determined using single-crystal X-ray diffraction data. The minerals are the two structural modifications of the compound with the ideal formula V$_{2}$Cu$_{24}$As$_{6}$S$_{32}$; they differ from each other in the occupancy of the interstitial position 2a. In colusite, this position is occupied by the V$^{5+}$ cations; in arsenosulvanite and V,As-germanite, by Cu$^{2+}$. A characteristic feature of the structures is the presence of octahedral [ $$T'$$ S$_{4}$]Cu$_{6}$ ( $$T'$$ = V, Cu) complexes not directly interacting with each other and lying inside the Laves polyhedra. In the structures of arsenosulvanite and V,As-germanite, a sulvanite framework consisting of interpenetrating Laves polyhedra $$T'$$ T$_{3}$S$_{4}$ ( $$T'$$ = V, Cu; T = Cu, As, Ge) has been found. The sulvanite framework is statistically distributed over the sphalerite matrix. The variable composition of the minerals is due to heterovalent isomorphism in the sphalerite position 6c. Charge disbalance arising from substitution of the pentavalent arsenic cations by cations of lower valence is compensated by the appearance of additional Cu$^{2+}$ cations. The nonstoichiometry of the compositions is explained by the presence of vacancies in the interstitial and sphalerite positions.
Starting Page	89
Ending Page	100
Page Count	12
File Format	PDF
ISSN	00224766
Journal	Journal of Structural Chemistry
Volume Number	43
Issue Number	1
e-ISSN	15738779
Language	English
Publisher	Kluwer Academic Publishers-Plenum Publishers
Publisher Date	2002-01-01
Publisher Place	New York
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Inorganic Chemistry Physical Chemistry Atoms, Molecules, Clusters and Plasmas
Content Type	Text
Resource Type	Article
Subject	Materials Chemistry Physical and Theoretical Chemistry Inorganic Chemistry

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