Summary
Joesmithite is a complex clinoamphibole which contains at least 14 components in its formula. Its ideal formula would be PbCa2 Mg3 Fe 3+2 (Si6Be2O22) (OH)2. It is monoclinic holosymmetric, an ordered derivative of theC2/m clinoamphiboles,a = 9.915(2),b = 17.951(4),c = 5.243(1)Å,β = 105.95(2)°, Z = 2, space groupP2/a, D(obs) = 3.83(1), D(cal) = 3.91 g cm-3. R = 0.056 for 2299 independent F0.
The cells of joesmithite and pargasitic amphibole were compared according to differences, Δ, in their structure cells. The same procedure was applied to the margarosanite, PbCa2Si3O9 and walstromite, BaCa2Si3O9 pairs. In both pairs, the anion positions differed by 0.2 Å at most, but the Pb/A, Pb/Ba differences ranged from 0.4 to 0.6 Å. The lone pair Pb2+ cation responds according to the bond valence sums of its coordinating anions compared with its closed core counterpart.
It appears that when the bond valence sums for the coordinating anions are different, Pb2+ moves toward the most underbonded anion. If the anion bond valence sums are equal for all vertices of the coordinating polyhedron (as in wulfenite, Pb2+Mo6+O4), then Pb2+ does not shift.
Zusammenfassung
Joesmithit ist ein komplex zusammengesetzter Klinoamphibol, der rumindest 14 Komponenten in seiner Formel aufweist. Die idealisierte Formel lautet PbCa2Mg3Fe 3+2 (Si6Be2O22)(OH)2. Er ist monoklin holoedrisch und von den geordnetenC2/m-Klinopyroxenen abgeleitet,a = 9,915(2),b = 17,951(4),c = 5,243(1) Å,ß = 105,95(2)°, Z = 2, RaumgruppeP2/a, D(beob) = 3,83(1), D(ber) = 3,91 g cm-3. R = 0,056 für 2299 unabhängige F0.
Die Elementarzellen von Joesmithit und einem pargasitischen Amphibol wurden in Bezug auf deren Struktur verglichen, ebenso jene von Margarosanit, PbCa2Si3O9, und Walstromit, BaCa2Si3O9, In beiden Paaren differieren die Positionen der Anionen um maximal 0,2 Å, die Unterschiede Pb/A = (Na, K, □) und Pb/Ba betragen 0,4 und 0,6 Å. Das ein einsames Elektronenpaar aufweisende Kation Pb2+ folgt den Bindungsstärken der koordinierenden Anionen im Vergleich zu den Pendents mit abgeschlossener Elektronenschale.
Differieren die Bindungsstärken der koordinierenden Anionen, bewegt sich Pb2+ offensichtlich auf das am schwächsten abgesättigte Anion zu. Falls die Summe der Bindungsstärken an den Anionen in allen Richtungen des Koordinationspolyeders gleich sind (wie im Wulfenit, Pb2+Mo6+O4), dann kommt es zu keiner Verschiebung des Pb-Atoms.
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Dedicated to Prof. Josef Zemann, Keeper of the flame of chemical crystallography
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Moore, P.B., Davis, A.M., Van Derveer, D.G. et al. Joesmithite, a plumbous amphibole revisited and comments on bond valences. Mineralogy and Petrology 48, 97–113 (1993). https://doi.org/10.1007/BF01163090
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DOI: https://doi.org/10.1007/BF01163090