Bulgakite, ideally Li2(Ca,Na)Fe2+7Ti2(Si4O12)2O2(OH)4(O,F)(H2O)2, and nalivkinite, ideally Li2NaFe2+7Ti2(Si4O12)2O2(OH)4F(H2O)2, are astrophyllite-supergroup minerals. Bulgakite is a new mineral from the Darai-Pioz alkaline massif in the upper reaches of the Darai-Pioz river, in the area of the joint Turkestansky, Zeravshansky, and Alaisky ridges, Tajikistan. Bulgakite was found in fenitized amphibole–quartz–feldspar rock with brannockite, sogdianite, bafertisite, albite, and titanite. Bulgakite is brownish orange, transparent in thin grains, and has a vitreous luster. Mohs hardness is 3, Dmeas. = 3.30(2) g/cm3, Dcalc. = 3.326 g/cm3. Bulgakite is biaxial (+) with refractive indices (λ = 589 nm) α = 1.695(3), β = 1.711(2), γ = 1.750(3); 2Vmeas. = 70(5)°, 2Vcalc. = 67°, strong dispersion: r > v. Cleavage is perfect parallel to {001} and moderate parallel to {010}. Chemical analysis by electron microprobe gave SiO2 35.63, Al2O3 0.95, Na2O 1.04, K2O 3.27, Cs2O 0.31, CaO 2.56, MgO 0.16, ZnO 0.15, FeO 29.24, MnO 7.14, TiO2 11.07, Nb2O5 0.49, ZrO2 0.37, SnO2 1.18, F 1.01, Li2O 1.36 (AAS), Rb2O 0.85 (AAS), (H2O)calc. 4.04, sum 100.38 wt.%, H2O was calculated from crystal-structure analysis. The empirical formula based on 31.94 (O + OH + F + H2O) pfu is (Li0.94K0.91Rb0.12Cs0.03)Σ2(Ca0.60Na0.40)Σ1(Fe2+5.34Mn1.32Li0.25Mg0.05Na0.04Zn0.02)Σ7.02 (Ti1.82Sn0.10Nb0.05Zr0.04)Σ2.01[(Si7.78Al0.24)Σ8.02O24]O2(OH)4(F0.70O0.30)[(H2O)0.941.06]Σ2, Z = 1. Bulgakite is triclinic, space group Pforumla, a 5.374(1), b 11.965(2), c 11.65(3) Å, α 113.457(8), β 94.533(8), γ 103.08(1)°, V 657.5(8) Å3. The six strongest reflections in the X-ray powder diffraction data [d (Å), I, (hkl)] are: 10.54, 100, (001); 3.50, 100, (003); 2.578, 100, (130); 2.783, 90, (1 forumla2); 1.576, 68, (3 forumla1, forumla2); 2.647, 55, ( forumla11). The crystal structure has been refined to R1 = 2.6% for 3592 unique Fo > 4σF) reflections. In the crystal structure of bulgakite, there are four [4]T sites, with <T–O> = 1.626 Å, occupied mainly by Si, with minor Al. The TO4 tetrahedra constitute the T4O12 astrophyllite ribbon. The [6]D site is occupied mainly by Ti, with <D–φ> = 1.965 Å (φ = O, F). The T4O12 astrophyllite ribbons and D octahedra constitute the H (Heteropolyhedral) sheet. In the O (Octahedral) sheet, there are four Fe2+-dominant [6]M(1–4) sites, with <M–φ> = 2.159 Å (φ = O, OH). Two H and the central O sheets form the HOH block, and adjacent HOH blocks link via a common anion (XPD) of two D octahedra. In the I (Intermediate) block between adjacent HOH blocks, there are two interstitial cation sites, A and B, and a W site, partly occupied by H2O. The A site splits into two partly occupied sites, [13]A(1) and [6]A(2), with A(1)–A(2) = 1.16 Å. The [6]A(2) site is occupied by Li with <A(2)–φ> = 2.285 Å (φ = O, F, H2O), and the [13]A(1) site is occupied by K, Rb, and Cs with <A(1)–φ> = 3.298 Å. The aggregate content of the A site is (Li0.94K0.91Rb0.12Cs0.03)Σ2, ideally Li2apfu. The [10]B site is occupied by (Ca0.60Na0.40) with <B–φ> = 2.593 Å. The W site is occupied by [(H2O)0.941.06]Σ2pfu. The mineral is named bulgakite after Lev Vasil'evich Bulgak (born 1955), Russian mineralogist, gemologist, and discoverer of several new minerals. The crystal structure of nalivkinite has been revised and refined to R1 = 4.52% for 3546 unique (Fo > 4σF) reflections: space group Pforumla, a 5.374(3), b 11.948(5), c 11.676(5) Å, α 113.360(6), β 94.538(8), γ 103.01(1)°, V 658.7(9) Å3, Z = 1, Dcalc. = 3.347 g/cm3. The revised empirical formula of nalivkinite is based on 32.14 (O + OH + F + H2O) pfu: (Li1.14K0.75Cs0.09Pb0.02)Σ2(Na0.71Ca0.29)Σ1(Fe2+5.62Mn0.90Zr0.08Na0.08Mg0.04Zn0.04)Σ6.76(Ti1.56Nb0.24Sn0.09Zr0.08Ta0.04)Σ2[(Si7.86Al0.15)Σ8.01O24]O2(OH)4F[(H2O)1.140.86]Σ2. The presence of H2O groups in the bulgakite and nalivkinite structures was confirmed by infrared spectroscopy. Bulgakite is a Ca-analogue of nalivkinite. Bulgakite and nalivkinite are related by the following substitution: 0.3 BCa2+ + 0.3 XO2– ↔ 0.3 BNa+ + 0.3 XF.

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