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Crystal structure of lindackerite, (Cu,Co,Ni)Cu₄(AsO₄)₂ (AsO₃OH)₂·9H₂O from Jáchymov, Czech Republic

Jií HYBLER^1,*, Petr ONDRU³, Ivana CíSAOVÁ², Václav PETÍEK¹ and Frantiek VESELOVSK³

¹ Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, CZ-182 21 Praha 8, Czech Republic
² Department of Inorganic Chemistry, Faculty of Sciences, Charles University, Hlavova 2030, CZ-128 43 Praha 2, Czech Republic
³ Czech Geological Survey, Klárov 3, CZ-118 21 Praha 1, Czech Republic

^* Corresponding author, e-mail: hybler{at}fzu.cz

Two crystals of lindackerite, ideally (Cu,Co,Ni)Cu₄(AsO₄)₂ (AsO₃OH)₂ . 9 H₂O from Jáchymov (formerly St. Joachimsthal), Czech Republic, were studied and found to be essentially isostructural. The microprobe analysis of the first sample yielded (in wt%): As 29.66, Cu 27.85, Co 1.50, Ni 0.83,O 39.96, sum 99.79, (Cu_0.43CO_o.26Ni_o.14) _)o.83 Cu_4.00 [(AsO₄) _1.66(AsO₃OH)_2.34] .9.24H₂O, P, a, = 6.440(2), b = 8.065(3), c= 10.411(5) Å, = 85.44(4)°, β = 79.38(3)°, = 84.65(3)°, V = 528.1(3) ų, Z=1, D_calc = 3.261 g/cm³. The structure was refined to R_obs = 5.03 %. The second crystal was an end member, without any Co, Ni yielded (in wt%): As 30.66, Cu31.76, Co<0.01, Ni<O.01, O39.30, sum 101.75, Cu_0.89 Cu_4.00[(AsO₄)_1.78 (AsO₃OH)2.22] .8.01 H₂O, = 6.415(1), b = 8.048(1), c = 10.332(1) Å, = 85.41(1), β = 79.50(1)°, = 84.71(1)°, V = 521.2(1) ų. Z = 1, D_calc = 3.312 g/cm³ was refined to R_obs= 5.29 %. The atomic arrangement in lindackerite is very similar to that of chudobaite and geigerite. There are three cationic positions, two As and 15 oxygen atoms. The bond-valence calculation reveals that one oxygen position represents OH group and 7 others water molecules. The substituting Co and Ni atoms enter presumably the special position at 1/2, O,O, denoted as M. Of other two positions Cul is five-coordinated in configuration of square pyramid, whereas Cu2 is octahedrally coordinated. Edge-sharing Cul pyramids and Cu2 octahedra form infinite bands parallel to [110]. The adjacent bands are linked together by two kinds of As-tetrahedra. As a result a layer parallel to (001) is formed. The adjacent layers are connected via M atoms. In addition, the M position is surrounded by eight half-occupied water molecules (Ow31-Ow34) in four independent positions. This arrangement can be interpreted as two interpenetrating octahedra (with common corners shared with As2 tetrahedra) turned by -45°. In chudobaite and geigerite only one of these alternative octahedra exists and respective positions are fully occupied. One "zeolitic" water molecule Owl is located in the interlayer space and is half-occupied. Of other two water molecules Ow4 forms one of apices of the Cu2 octahedron, and Ow2 is located near the base of the Cul pyramid, but is rather distant (2.79(1) Å) to complete octahedral coordination.

Key-words: lindackerite, copper arsenate, crystal structure, Jæchymov.

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