Kozłowskiite, ideally Ca4Fe2+Sn3(Si2O7)2(Si2O6OH)2, a new kristiansenite-type mineral from Szklarska Poręba, Lower Silesia, Poland

Abstract

AbstractKozłowskiite, ideally Ca4(Fe2+Sn3)(Si2O7)2(Si2O6OH)2, is a new mineral isostructural with kristiansenite and silesiaite, found as a band in the core of a zoned silesiaite–kristiansenite crystal from the granitic pegmatite at Szklarska Poręba, Lower Silesia, Poland. In tiny pieces kozłowskiite is pale brownish, with a calculated density of 3.775 g⋅cm–3 and a mean refractive index ~1.727. The triclinic crystal structure was determined with space-group symmetry C1: a = 10.0183(2), b = 8.3861(1), c = 13.3395(2) Å, α = 89.956(1), β = 109.039(2), γ = 89.979(1)° and V = 1059.40(3) Å3, although, similarly to kristiansenite, it is metrically monoclinic (Laue group 2/m) with α and γ angles equal to 90° and a = 10.0170(3), b = 8.3860(2), c = 13.3421(4) Å, β = 109.050(3)° and V = 1059.40(5) Å3. The seven strongest reflections in the calculated powder X-ray diffraction pattern are [d in Å (I) hkl]: 5.190 (73.2) 111, 1$\bar{1}$1; 4.569 (30.0) $\bar{2}$02; 3.153 (64.7) 004; 3.094 (28.1) $\bar{3}$11, $\bar{3}\bar{1}$1; 3.089 (100) $\bar{2}\bar{2}$2, $\bar{2}$22; 2.595 (27.2) 2$\bar{2}$2, 222; and 2.141 (30.6) $\bar{3}$31, $\bar{3}\bar{3}$1. Electron microprobe analysis gave (in wt.%) SiO2 39.46, ZrO2 0.35, SnO2 31.13, Al2O3 0.35, Sc2O3 2.65, total Fe as Fe2O3 5.06 (= Fe2O3calc. 2.26; FeOcalc. 2.52), MnO 0.71, CaO 18.42 and H2Ocalc. 1.48, sum 99.33. The empirical formula on the basis of 26O + 2(OH) and 16 cations (Z = 2) is Ca4.00(Sn2.52Sc0.47Fe2+0.43Fe3+0.34Mn2+0.12Al0.08Zr0.03)Σ4.00(Si2.00O7)2(Si2.00O6OH)2. The crystal structure of kozłowskiite was refined to an R1 = 2.12% for 4887 reflections with Io>2σI. The Ca and Si sites are occupied solely by Ca and Si, respectively, and three of four M sites: M2, M3 and M4, are dominated by Sn. Four hydrogen atoms present in the kozłowskiite unit cell are shared among the O17–O27 and O47–O37 oxygen atoms where O17 and O47 are OH groups forming relatively strong hydrogen bonds.