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Batagayite, CaZn2(Zn,Cu)6(PO4)4(PO3OH)3·12H2O, a new phosphate mineral from Këster tin deposit (Yakutia, Russia): occurrence and crystal structure

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Batagayite, CaZn2(Zn,Cu)6(PO4)4(PO3OH)3·12H2O, is a new secondary phosphate mineral from the Këster deposit, Arga-Ynnykh-Khai massif, NE Yakutia, Russia. It is monoclinic, P21, a = 8.4264(4), b = 12.8309(6), c = 14.6928(9) Å, β = 98.514(6)o, V = 1571.05(15) Å3 and Z = 2 (from single-crystal X-ray diffraction data). Batagayite crystals are blades up to 2 mm long, flattened on {001} and elongated on [100]; blades often grow in radial aggregates. Associated minerals are arsenolite, native copper, epifanovite, fluorapatite, libethenite, Na-analogue of batagayite, pseudomalachite, quartz, sampleite, tobermorite, and Mg-analogue of hopeite. The streak is white and the luster is vitreous. The mineral is brittle and has a perfect cleavage on {001}, no parting was observed. The Mohs hardness is 3. Density, determined by the float-sink method in Clerici solution, is 2.90(3) g/cm3, and the calculated density is 3.02 g/cm3 (using the empirical formula and single-crystal unit-cell parameters). Batagayite is biaxial, optically negative, α = 1.566 ± 0.002, β = 1.572 ± 0.002, γ = 1.573 ± 0.002 at 589 nm. 2V meas. = 40(5)°, 2V calc = 44.3°. Optical orientation: Z is perpendicular to (001), further details unclear. No dispersion or pleochroism were observed. The mean chemical composition determined by electron microprobe is: Na2O 0.31, MgO 1.39, Al2O3 0.55, SiO2 0.48, P2O5 34.37, K2O 0.17, CaO 2.76, MnO 1.03, CuO 5.80, ZnO 35.62, CdO 0.24 wt%. The H2O content estimated from the crystal-structure refinement is 16.83 wt%, giving a total of 99.55 wt%. The empirical formula calculated on the basis of P + Si = 7 is (Zn6.22Cu1.04Ca0.70Mg0.49Mn0.21Al0.15Na0.14K0.05Cd0.03)Σ9.03(P6.89Si0.11)Σ7.00O24.91(OH)3.09·12.10H2O. The mineral easily dissolves in 10% room-temperature HCl. The eight diagnostic lines in the X-ray powder-diffraction pattern are (I-d[Å]-hkl): 100-14.59-001, 25-6.34-012, 11-6.02-111, 37-4.864-003, 13-4.766-112, 20-3.102-1 \(\overline {2} \:\overline {4}\), 11-2.678-2 \(\overline {3} \:\overline {3}\), 16-2.411-044. The crystal structure of batagayite was solved by direct methods and refined to R 1 = 0.069 for 3847 independent reflections with F o > 4σ(F o). It is based upon complex heteropolyhedral [M 8(PO4)4(PO3OH)3(H2O)9]2− layers parallel to the (001) plane. The layer can be considered as consisting of three sublayers, one A and two B. The central A layer has the composition [M 4(PO4)4(H2O)4]4− and consists of the zigzag chains of edge-sharing (MO6) octahedra running parallel to the a axis and linked into layers by sharing peripheral O atoms. The (PO4) tetrahedra are attached above and below the holes created by the linkage of zigzag octahedral chains. The B sublayer consists of chains of (ZnO4) and (PO3OH) tetrahedra. The interlayer space is occupied by the Ca2+ cations and H2O molecules. Batagayite is a secondary low-temperature mineral formed as a result of alteration of primary minerals such as native copper and fluorapatite. On the basis of its structural complexity calculated as 1058.257 bits/cell (taking into account contributions from H atoms), batagayite should be considered as a very complex mineral. The high complexity of batagayite is due to its high hydration state and the modular character of its structure, which contains both octahedral-tetrahedral layers and tetrahedral chains.

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The manuscript was essentially improved following reviews by Anthony R. Kampf and Gerald Giester, and editorial efforts of Maarten A.T.M. Broekmans. This research was supported by the Russian Science Foundation, grant 14-17-00071.

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Correspondence to Sergey V. Krivovichev.

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Editorial handling: M. A.T.M. Broekmans

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Yakovenchuk, V.N., Pakhomovsky, Y.A., Konopleva, N.G. et al. Batagayite, CaZn2(Zn,Cu)6(PO4)4(PO3OH)3·12H2O, a new phosphate mineral from Këster tin deposit (Yakutia, Russia): occurrence and crystal structure. Miner Petrol 112, 591–601 (2018).

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