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Crystal chemistry of lead oxide chlorides. I. Crystal structures of synthetic mendipite, Pb₃O₂Cl₂, and synthetic damaraite, Pb₃O₂(OH)Cl

¹ Department of Crystallography, Faculty of Geology, St. Petersburg State University, University Emb. 7/9, St. Petersburg 199034, Russia. – e-mail: sergey{at}cryst.geol.pu.ru
² Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick, University of Notre Dame, Notre Dame IN 46556–0767, USA

The crystal structure of synthetic damaraite, Pb₃O₂(OH)Cl (orthorhombic, Pmc2₁, a = 5.8052(7), b = 6.9025(8), c = 15.141(2) Å, V = 606.7(1) ų has been solved by direct methods and refined to R1 = 0.039. The crystal structure of synthetic mendipite, Pb₃O₂Cl₂ (orthorhombic, Pnma, a = 11.879(7), b = 5.808(4), c = 9.505(6) Å, V = 655.8(7) ų) has been refined to R1 = 0.049. Both structures are based on [O₂Pb₃] double chains of edgesharing OPb₄ oxocentered tetrahedra that extend parallel to the a and b axes in damaraite and mendipite, respectively. In mendipite, the chains occur in two mutually perpendicular orientations, whereas, in damaraite, the chains occur in two orientations inclined to each other by 50°. In mendipite, the chains are linked through weak Pb-Cl bonds only, whereas, in damaraite, the [O₂Pb₃] chains are linked through OH(3) groups to form an [Pb₃O₂](OH) sheet that is parallel to (010). Additional OH(4) groups in damaraite are attached to the [O₂Pb₃] double chains. The OH groups in damaraite form two short (OH)-Pb bonds that results in (OH)Pb₂ dimers. It is shown that (consistent with previous studies) OH^–-Cl^– substitution is likely to occur in damaraite and possible structural schemes for this substitution are outlined. Both mendipite and damaraite are members of the structural family of minerals and synthetic compounds that are based upon [O₂Pb₃] double chains of (OPb₄) oxocentered tetrahedra.

Key-words: lead oxide chlorides, mendipite, damaraite, oxocentered tetrahedra, crystal structure.

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