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Crystal chemistry of basic lead carbonates. II. Crystal structure of synthetic ‘plumbonacrite’

S. V. Krivovichev^*, and P. C. Burns

Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick, University of Notre Dame, Notre Dame IN 46556-0767, USA

^* E-mail: sergey{at}cryst.geol.pu.ru

The crystal structure of synthetic ‘plumbonacrite’, Pb₅O(OH)₂(CO₃)₃, hexagonal, P6₃cm, a = 9.0921(7), c = 24.923(3) Å, V = 1784.3(3) Å ³, Z = 6, has been solved by direct methods and refined to R = 0.049. There are six symmetrically independent Pb²⁺ positions in the structure, the coordination polyhedra of which are strongly distorted due to the effect of s² lone-electron pairs on the Pb²⁺ cations. The Pb(6) position is disordered with a Pb–Pb distance of 1.24 Å. The structure of ‘plumbonacrite’ is built from complex Pb–O layers parallel to the (001) plane similar to those observed in polymorphs of Pb₄(OH)₂(SO₄)(CO₃)₂. The structure of these layers can be described in terms of Pb–O,OH motifs and CO₃ groups. The smallest structural subunit is the oxocentred [OPb₄] tetrahedron that shares three of its Pb-Pb edges with three [(OH)Pb₃] distorted triangles to form [O(OH)₃Pb₇] clusters. These clusters are surrounded by CO₃ groups, forming more complex clusters. Due to the disorder in the Pb(6) site, the clusters comprising this site are linked with each other via OH(10) groups to give continuous sheets of Pb–O,OH bonds which are parallel to the (001) plane. The [O(OH)₃Pb₇] clusters in ‘plumbonacrite’ may be important in more complex Pb carbonate oxo/hydroxo complexes that may exist in aqueous environments.

KEYWORDS: ‘plumbonacrite’, lead carbonate, lead oxo/hydroxo clusters

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