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The crystal structure and chemistry of mereheadite

¹ Department of Crystallography, Geological Faculty, Saint-Petersburg State University, University Emb. 7/9, St. Petersburg, 199034, Russia
² Institute of Silicate Chemistry, Russian Academy of Sciences, nab. Makarova 6, St. Petersburg, 199034, Russia
³ The Drey, Allington Track, Allington, Salisbury SP4 0DD, UK
⁴ Department of Mineralogy, Natural History Museum, Cromwell Road, London SW7 5BD, UK
⁵ Department of Chemistry, Loughborough University, Leicestershire LE11 3TU, UK

^* E-mail: skrivovi{at}mail.ru

The crystal structure of mereheadite (monoclinic, Cm, a = 17.372(1), b = 27.9419(19), c = 10.6661(6) Å, β = 93.152(5)^o, V = 5169.6(5) ų) has been solved by direct methods and refined to R₁ = 0.058 for 6279 unique observed reflections. The structure consists of alternating Pb-O/OH blocks and Pb-Cl sheets oriented parallel to the (201) plane and belongs to the 1:1 type of lead oxide halides with PbO blocks. It contains 30 symmetrically independent Pb positions, 28 of which belong to the PbO blocks, whilst two positions (Pb12 and Pb16) are located within the tetragonal sheets of the Cl^- anions. Mereheadite is thus the first naturally occurring lead oxychloride mineral with inter-layer Pb ions. The coordination configurations of the Pb atoms of the PbO blocks are distorted versions of the square antiprism. In one half of the coordination hemisphere, they are coordinated by hard O^2- and OH^- anions whose number varies from three to four, whereas the other coordination hemisphere invariably consists of four soft Cl^- anions located at the vertices of a distorted square. The Pb12 and Pb16 atoms in between the PbO blocks have an almost planar square coordination of four Cl^- anions. These PbCl₄ squares are complemented by triangular TO₃ groups (T = B, C) so that a sevenfold coordination is achieved. The Pb-O/OH block in mereheadite can be obtained from the ideal PbO block by the following list of procedures: (1) removal of some PbO₄ groups that results in the formation of square-shaped vacancies; (2) insertion of TO₃ groups into these vacancies; (3) removal of some Pb atoms (that correspond to the Pb1A and Pb2A sites), thus transforming coordination of associated O sites from tetrahedral OPb₄ to triangular OHPb₃; and (4) replacement of two O^2- anions by one OH^- anion with twofold coordination; this results in formation of the 1 x 2 elongated rectangular vacancy. The structural formula that can be derived on the basis of the results of single-crystal structure determination is Pb₄₇O₂₄(OH)₁₃Cl₂₅(BO₃)₂(CO₃). Welch et al. (1998) proposed the formula Pb₂O(OH)Cl for mereheadite, which assumes that neither borate nor carbonate is an essential constituent of mereheadite and their presence in the mineral is due to disordered replacements of Cl^- anions. However, our study demonstrates that this is not the case, as BO₃ and CO₃ groups have well-defined structural positions confined in the vacancies of the Pb-O/OH blocks and are therefore essential constituents. Our results also show that mereheadite is not a polymorph of blixite, but is in fact related to symesite. Symesite thus becomes the baseline member of a group of structurally-related minerals.

KEYWORDS: mereheadite, crystal structure, lead oxychlorides, borate, carbonate, Merehead, Mendips, symesite