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The crystal structure of quintinite-2H-3c, [Mg4Al2(OH)12](CO3)(H2O)3, from the Kovdor alkaline massif, Kola peninsula, Russia, was solved by direct methods and refined to an agreement index (R1) of 0.055 for 484 unique reflections with |Fo| ≥ 4σF. The mineral is rhombohedral, R32, a = 5.2745(7), c = 45.36(1) Å. The diffraction pattern of the crystal has strong and sharp Bragg reflections having h–k = 3n and l = 3n and lines of weak superstructure reflections extended parallel to c* and centred at h–k ≠ 3n. The structure contains six layers within the unit cell with the layer stacking sequence of …AC=CA=AC=CA=AC=CA… The Mg and Al atoms are ordered in metal hydroxide layers to form a honeycomb superstructure. The full superstructure is formed by the combination of two-layer stacking sequence and Mg-Al ordering. This is the first time that a long-range superstructure in carbonate-bearing layered double hydroxide (LDH) has been observed. Taking into account Mg-Al ordering, the unique layer sequence can be written as …=Ab1C=Cb1A=Ab2C=Cb2A=Ab3C=Cb3A=… The use of an additional suffix is proposed in order to distinguish between LDH polytypes having the same general stacking sequence but with different c parameters compared with the ‘standard’ polytype. According to this notation, the quintinite studied here can be described as quintinite-2H-3c or quintinite-2H-3c[6R], indicating the real symmetry.

The Kovdor baddeleyite-apatite-magnetite deposit in the Kovdor phoscorite-carbonatite pipe is situated in the western part of the zoned alkali-ultrabasic Kovdor intrusion (NW part of the Fennoscandinavian shield; Murmansk Region, Russia). We describe major intrusive and metasomatic rocks of the pipe and its surroundings using a new classification of phoscorite-carbonatite series rocks, consistent with the IUGS recommendation. The gradual zonation of the pipe corresponds to the sequence of mineral crystallization (forsterite-hydroxylapatite-magnetite-calcite). Crystal morphology, grain size, characteristic inclusions, and composition of the rock-forming and accessory minerals display the same spatial zonation pattern, as do the three minerals of economic interest, i.e. magnetite, hydroxylapatite, and baddeleyite. The content of Sr, rare earth elements (REEs), and Ba in hydroxylapatite tends to increase gradually at the expense of Si, Fe, and Mg from early apatite-forsterite phoscorite (margins of the pipe) through carbonate-free, magnetite-rich phoscorite to carbonate-rich phoscorite and phoscorite-related carbonatite (inner part). Magnetite displays a trend of increasing V and Ca and decreasing Ti, Mn, Si, Cr, Sc, and Zn from the margins to the central part of the pipe; its grain size initially increases from the wall rocks to the inner part and then decreases towards the central part; characteristic inclusions in magnetite are geikielite within the marginal zone of the phoscoritecarbonatite pipe, spinel within the intermediate zone, and ilmenite within the inner zone. The zoning pattern seems to have formed due to both cooling and rapid degassing (pressure drop) of a fluid-rich magmatic column and subsequent pneumatolytic and hydrothermal processes.

Quintinite-1M, [Mg4Al2(OH)12](CO3)(H2O)3, is the first monoclinic representative of both synthetic and natural layered double hydroxides (LDHs) based on octahedrally coordinated di- and trivalent metal cations. It occurs in hydrothermal veins in the Kovdor alkaline massif, Kola peninsula, Russia. The structure was solved by direct methods and refined to R1 = 0.031 on the basis of 304 unique reflections. It is monoclinic, space group C2/m, a = 5.266(2), b = 9.114(2), c = 7.766(3) Å, β = 103.17(3)°, V = 362.9(2) Å3. The diffraction pattern of quintinite-1M contains sharp reflections corresponding to the layer stacking sequence characteristic of the 3R rhombohedral polytype, and rows of weak superlattice reflections superimposed upon a background of streaks of modulated diffuse intensity parallel to c*. These superlattice reflections indicate the formation of a 2-D superstructure due to Mg-Al ordering. The structure consists of ordered metal hydroxide layers and a disordered interlayer. As the unit cell contains exactly one layer, the polytype nomenclature dictates that the mineral be called quintinite-1M. The complete layer stacking sequence can be described as …=Ac1B=Ba1C=Cb1A=… Quintinite-1M is isostructural with the monoclinic polytype of [Li2Al4(OH)12](CO3)(H2O)3.

The crystals of lamprophyllite-2M and lamprophyllite-2O were found coexisting in an ussingite-microcline-sodalite veins in the Alluaiv Mt., Lovozero alkaline massif, in association with ussingite, aegirine, microcline, sodalite, albite, manganneptunite, vuonnemite, sphalerite, lomonosovite and betalomonosovite. The chemical composition of the polytypes corresponds to the formula (Sr 1.18 Na 0.66 Ca 0.12) S1.96 Na (Na 1.30 Mn 0.36 Fe 0.22 Mg 0.12) S2.00 Ti 3 O 2 (Si 2 O 7) 2 (OH) 2. The structures of lamprophyllite-2M (C2/m, a = 19.215(5), b = 7.061(2), c = 5.3719(15) Å, b = 96.797(4) o , V = 723.7(4) Å 3) and lamprophyllite-2O (Pnmn, a = 19.128(4), b = 7.0799(14), c = 5.3824(11) Å, V = 728.9(3) Å 3) have been refined to R = 0.040 for 688 reflections (|F o | 4s F) and to R = 0.084 for 571 reflections (|F o | 4s F), respectively. The structures of both polytypes are based on the HOH layer consisting of a central O sheet of edge-sharing Na(1)O 6 , Na(2)O 6 and Ti(2)O 6 octahedra sandwiched between two heterophyllosilicate H sheets. The H sheet is built by corner-sharing of Ti(1)O 5 square pyramids and Si 2 O 7 groups and consists of two types of rings of polyhedra: (i) six-membered rings (6R) formed by two Si 2 O 7 groups and two TiO 5 square pyramids and (ii) four-membered rings (4R) formed by two silicate tetrahedra and two TiO 5 square pyramids. The Sr atom is located in the interlayer and is coordinated by six anions from 6R of the upper H sheet and four anions from 4R of the lower H sheet. The difference between monoclinic and orthorhombic lamprophyllites can be described in terms of different orientations of HOH layers. Whereas in lamprophyllite-2M, all HOH layers are in the same orientation, in lamprophyllite-2O, two adjacent layers are in different orientations.

Two quintinite polytypes, 3R and 2T, which are new for the Kovdor alkaline-ultrabasic complex, have been structurally characterized. The crystal structure of quintinite-2T was solved by direct methods and refined to R1 = 0.048 on the basis of 330 unique reflections. The structure is trigonal, P$\bar 3$c1, a = 5.2720(6), c = 15.113(3) Å and V = 363.76(8) Å3. The crystal structure consists of [Mg2Al(OH)6]+ brucite-type layers with an ordered distribution of Mg2+ and Al3+ cations according to the $\sqrt 3 $ × $\sqrt 3 $ superstructure with the layers stacked according to a hexagonal type. The complete layer stacking sequence can be described as …=Ab1C = Cb1A=…. The crystal structure of quintinite-3R was solved by direct methods and refined to R1 = 0.022 on the basis of 140 unique reflections. It is trigonal, R$\bar 3$m, a = 3.063(1), c = 22.674(9) Å and V = 184.2(1) Å3. The crystal structure is based upon double hydroxide layers [M2+,3+(OH)2] with disordered distribution of Mg, Al and Fe and with the layers stacked according to a rhombohedral type. The stacking sequence of layers can be expressed as …=АB = BC = CA=… The study of morphologically different quintinite generations grown on one another detected the following natural sequence of polytype formation: 2H → 2T → 1M that can be attributed to a decrease of temperature during crystallization. According to the information-based approach to structural complexity, this sequence corresponds to the increasing structural information per atom (IG): 1.522 → 1.706 → 2.440 bits, respectively. As the IG value contributes negatively to the configurational entropy of crystalline solids, the evolution of polytypic modifications during crystallization corresponds to the decreasing configurational entropy. This is in agreement with the general principle that decreasing temperature corresponds to the appearance of more complex structures.

Two crystals of Mg, Al-disordered quintinite-2H (Q1 and Q2), [Mg4Al2(OH)12](CO3)(H2O)3, from the Kovdor alkaline massif, Kola peninsula, Russia, have been characterized chemically and structurally. Both crystals have hexagonal symmetry, P63/mcm, a = 3.0455(10)/3.0446(9), c = 15.125(7)/15.178(5) Å, V = 121.49(8)/121.84(6) Å3. The structures of the two crystals have been solved by direct methods and refined to R1 = 0.046 and 0.035 on the basis of 76 and 82 unique observed reflections for Q1 and Q2, respectively. Diffraction patterns obtained using an image-plate area detector showed the almost complete absence of superstructure reflections which would be indicative of the Mg-Al ordering in metal hydroxide layers, as has been observed recently for other quintinite polytypes. The crystal structures are based on double hydroxide layers [M(OH)2] with an average disordered distribution of Mg2+ and Al3+ cations. Average <M–OH> bond lengths for the metal site are 2.017 and 2.020 Åfor Q1 and Q2, respectively, and are consistent with a highly Mg-Al disordered, average occupancy. The layer stacking sequence can be expressed as …=AC=CA=…, corresponding to a Mg-Al-disordered 2H polytype of quintinite. The observed disorder is probably the result of a relatively high temperature of formation for the Q1 and Q2 crystals compared to ordered polytypes. This suggestion is in general agreement with the previous observations which demonstrated, for the Mg-Al system, a higher-temperature regime of formation of the hexagonal (or pseudo-hexagonal in the case of quintinite-2H-3c) 2H polytype in comparison to the rhombohedral (or pseudo-rhombohedral in the case of quintinite-1M) 3R polytype.