The crystal structure of munakataite, Pb_2Cu_2(Se^(4+)O_3)(SO_4)(OH)_4, from Otto Mountain, San Bernardino County, California, USA

Abstract

Munakataite, Pb_2Cu_2(Se^(4+)O_3)(SO_4)(OH)_4, has been found in association with a variety of rare secondary Te minerals at Otto Mountain, San Bernardino County, California, USA. It is very rare and occurs as subparallel bundles of blue needles up to 1 mm long. Electron microprobe analyses provided the empirical formula Pb_(1.96)Cu_(1.60)[(Se^(4+)_(0.89)S_(0.11)_(∑1)O_3](SO_4)[(OH)_(3.34)(H_2O)_(0.66)]_(∑4). Munakataite is monoclinic, space group P2_1/m, with cell parameters a = 9.8023(26), b = 5.6751(14), c = 9.2811(25) Å , β = 102.443(6), V = 504.2(2) Å^3 and Z = 2. The crystal structure, solved by direct methods and refined to R_1 = 0.0308 for 544 F_o > 4σF reflections, consists of Jahn-Teller-distorted Cu^(2+)O_6 square bipyramids, which form chains along b by sharing trans edges across their square planes. The chains are decorated by SO_4 tetrahedra and Se^4+O_3 pyramids, which bond to apical corners of adjacent bipyramids. The chains are linked to one another via bonds to two different PbO_9 polyhedra, only one of which exhibits one-sided coordination typical of Pb^(2+) with a stereochemically active 6s^2 lone-electron-pair. Munakataite is isostructural with schmiederite and the structure is closely related to that of linarite.

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