The new mineral calciolangbeinite, ideally K2Ca2(SO4)3, is the Ca-dominant analogue of langbeinite. It occurs in sublimates at the Yadovitaya fumarole on the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure eruption, Tolbachik volcano, Kamchatka, Russia. The mineral is associated with langbeinite, piypite, hematite, rutile, pseudobrookite, orthoclase, lyonsite, lammerite, cyanochroite and chlorothionite. Calciolangbeinite occurs as tetrahedral to pseudo-octahedral crystals, which are bounded by {111} and {111İ}, and as anhedral grains up to 1 mm in size, aggregated into clusters up to 2 mm across, and forming crusts covering areas of up to 1.5×1.5 cm on the surface of volcanic scoria. Late-stage calciolangbeinite occurs in complex epitaxial intergrowths with langbeinite. Calciolangbeinite is transparent and colourless with white streak and vitreous lustre. Its Mohs' hardness is 3–3½. It is brittle, has a conchoidal fracture and no obvious cleavage. The measured and calculated densities are Dmeas = 2.68(2) and Dcalc = 2.74 g cm−3, respectively. Calciolangbeinite is optically isotropic with n = 1.527(2). The chemical composition of the holotype specimen is Na2O 0.38, K2O 21.85, MgO 6.52, CaO 16.00, MnO 0.27, FeO 0.08, Al2O3 0.09, SO3 55.14, total 100.63 wt.%. The empirical formula, calculated on the basis of twelve oxygen atoms per formula unit, is K2.01(Ca1.24Mg0.70Na0.05Mn0.02Fe0.01Al0.01)Σ2.03S3.00O12. Calciolangbeinite is cubic, space group P213, a = 10.1887(4) Å, V = 1057.68(4) Å3 and Z = 4. The strongest reflections in the X-ray powder pattern [listed as (d,Å(I)(hkl)] are 5.84(8)(111); 4.54(9)(120); 4.15(27)(211); 3.218(100)(310,130); 2.838(8)(230,320), 2.736(37)(231,321), 2.006(11)(431,341), 1.658(8)(611,532,352). The crystal structure was refined from single-crystal X-ray diffraction data to R = 0.0447. The structure is based on the langbeinite-type three-dimensional complex framework, which is made up of (Ca,Mg)O6 octahedra (Ca and Mg are disordered) and SO4 tetrahedra. Potassium atoms occupy two sites in voids in the framework; K(1) cations are located in ninefold polyhedra whereas K(2) cations are sited in significantly distorted octahedra. Calciolangbeinite and langbeinite are isostructural and form a solid-solution series.

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