Philipsburgite has been redefined as the intermediate member of the goldhillite–philipsburgite–kipushite isomorphous series with the ideal formula Cu5Zn[(AsO4)(PO4)](OH)6⋅H2O due to the site-selective As–P substitution. The new mineral goldhillite, ideally Cu5Zn(AsO4)2(OH)6⋅H2O [or Cu5Zn(AsO4)(AsO4)(OH)6⋅H2O], is the arsenate end-member of this series. Goldhillite occurs on fracture surfaces in a rock comprised mostly of quartz with iron hydroxides in association with mixite, cornwallite and conichalcite. Goldhillite forms transparent, bright emerald-green, tabular crystals with vitreous lustre, flattened on {100}, up to 1 mm across and in rosettes up to 1.5 mm. The mineral is brittle with uneven fracture and perfect cleavage on {100}; the Mohs hardness is 3.5. The calculated density for the holotype is 4.199 g cm–3. The Raman spectrum is consistent with the presence of H2O-molecules, OH-groups, AsO4 tetrahedra and traces of PO4. Electron microprobe analyses of goldhillite (H2O content based on the crystal structure) provided: CuO 48.91, ZnO 13.18, As2O5 26.06, P2O5 3.25, H2O 8.97, total 100.37 wt.%. The empirical formula for goldhillite based on O = 15 apfu is (Cu4.69Zn1.23)Σ5.92(As0.86P0.18O4)2(OH)5.61⋅H2O. The crystal structures of goldhillite and philipsburgite were determined using single-crystal X-ray diffraction data and refined to R1 = 0.054 (for 2365 I > 2σI reflections) and 0.052 (for 2308 I > 2σI reflections), respectively. Goldhillite is monoclinic, P21/c, a = 12.3573(5), b = 9.2325(3), c = 10.7163(4) Å, β = 97.346(4)°, V = 1212.59(8) Å3 and Z = 4. Philipsburgite is monoclinic, P21/c, a = 12.3095(9), b = 9.2276(3), c = 10.7195(3) Å, β = 97.137(7)°, V = 1208.16(10) Å3 and Z = 4. The strongest lines of the powder X-ray diffraction pattern of goldhillite [d, Å (I, %)(hkl)] are: 4.09 (28)(300), 3.41 (23)(12$\bar{2}$, 221, 311), 2.57 (100)(132, 11$\bar{4}$, 20$\bar{4}$), 2.17 (18)(42$\bar{3}$, 332), 1.95 (22)(432) and 1.54 (20)(13$\bar{6}$, 060). Goldhillite is named after its type locality, the Gold Hill mine, Tooele County, Utah, USA.

The complexities of chemical composition and crystal structure are fundamental characteristics of minerals that have high relevance to the understanding of their stability, occurrence and evolution. This review summarises recent developments in the field of mineral complexity and outlines possible directions for its future elaboration. The database of structural and chemical complexity parameters of minerals is updated by H-correction of structures with unknown H positions and the inclusion of new data. The revised average complexity values (arithmetic means) for all minerals are 3.54(2) bits/atom and 345(10) bits/cell (based upon 4443 structure reports). The distributions of atomic information amounts, chemIG and strIG, versus the number of mineral species fit the normal modes, whereas the distributions of total complexities, chemIG,total and strIG,total, along with numbers of atoms per formula and per unit cell are log normal. The three most complex mineral species known today are ewingite, morrisonite and ilmajokite, all either discovered or structurally characterised within the last five years. The most important complexity-generating mechanisms in minerals are: (1) the presence of isolated large clusters; (2) the presence of large clusters linked together to form three-dimensional frameworks; (3) formation of complex three-dimensional modular frameworks; (4) formation of complex modular layers; (5) high hydration state in salts with complex heteropolyhedral units; and (6) formation of ordered superstructures of relatively simple structure types. The relations between symmetry and complexity are considered. The analysis of temporal dynamics of mineralogical discoveries since 1875 with the step of 25 years show the increasing chemical and structural complexities of human knowledge of the mineral kingdom in the history of mineralogy. In the Earth's history, both diversity and complexity of minerals experience dramatic increases associated with the formation of Earth's continental crust, initiation of plate tectonics and the Great Oxidation event.

Dobrovolskyite, Na4Ca(SO4)3, is a new sulfate mineral from the Great Tolbachik fissure eruption, Kamchatka peninsula, Russia. It occurs as aggregates of tabular crystals up to 1–2 mm in maximum dimension, with abundant gas inclusions. The empirical formula calculated on the basis of O = 12 is (Na3.90K0.10)Σ4(Ca0.45Mg0.16Cu0.12Na0.10)Σ0.83S3.08O12. The crystal structure of dobrovolskyite was determined using single-crystal X-ray diffraction data as: trigonal, R3, a = 15.7223(2), c = 22.0160(5) Å, V = 4713.1(2) Å3, Z = 18 and R1 = 0.072. The Mohs’ hardness is 3.5. The mineral is uniaxial (+), with ω = 1.489(2) and ɛ = 1.491(2) (λ = 589 nm). The seven strongest lines of the powder X-ray diffraction pattern [d, Å (I, %)(hkl)] are: 11.58(40)(101); 5.79(22)(202); 4.54(18)(030); 3.86(88)(033); 3.67(32)(006); 2.855(50)(306); and 2.682(100)(330). The mineral is named in honour of Prof. Dr. Vladimir Vitalievich Dolivo-Dobrovolsky (1927–2009), one of the leading Russian scientists in the field of petrology, crystal optics and crystal chemistry. The crystal structure of dobrovolskyite can be described as composed of three symmetrically independent rods running parallel to the c axis. The rods consist of six octahedral–tetrahedral [Na(SO4)6]11– or [Ca(SO4)6]10– clusters of central octahedra sharing common corners with six adjacent SO4 tetrahedra. Alternatively, the crystal structure of the mineral can be described as a 12-layer ABACABACABAC eutactic array of Na+ and Ca2+ cations, and vacancies with disordered (SO4) tetrahedra in interstices. Dobrovolskyite and similar minerals probably formed upon cooling of a high-temperature phase with disordered cation and anion arrangements.

Hydrotalcite, ideally [Mg6Al2(OH)16](CO3)(H2O)4, was studied in samples from Dypingdal, Snarum, Norway (3R and 2H), Zelentsovskaya pit (2H) and Praskovie–Evgenievskaya pit (2H) (both Southern Urals, Russia), Talnakh, Siberia, Russia (3R), Khibiny, Kola, Russia (3R), and St. Lawrence, New York, USA (3R and 2H). Two polytypes, 3R and 2H (both ‘classical’), were confirmed on the basis of single-crystal and powder X-ray diffraction data. Their chemical composition was studied by electron-microprobe analysis, infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. The crystal structure of hydrotalcite-3R was solved by direct methods in the space group R$ {\bar 3} $m on three crystals (two data collections at 290 K and one at 120 K). The unit-cell parameters are as follows (290/290/120 K): a = 3.0728(9)/3.0626(3)/3.0617(4), c = 23.326(9)/23.313(3)/23.203(3) Å and V = 190.7(1)/189.37(4)/188.36(4) Å3. The crystal structures were refined on the basis of 304/150/101 reflections to R1 = 0.075/0.041/0.038. Hydrotalcite-2H crystallises in the P63/mmc space group; unit-cell parameters for two crystals are (data collection at 290 K and 93 K): a = 3.046(1)/3.0521(9), c = 15.447(6)/15.439(4) Å, V = 124.39(8)/124.55(8) Å3. The crystal structures were refined on the basis of 160/142 reflections to R1 = 0.077/0.059. This paper reports the first single-crystal structure data on hydrotalcite. Hydrotalcite distribution in Nature, diagnostic features, polytypism, interlayer topology and localisation of M2+–M3+ cations within metal hydroxide layers are discussed.

Rumseyite, ideally [Pb2OF]Cl, is a new mineral species which is associated with calcite, cerussite, diaboleite, hydrocerussite and undifferentiated Mn oxides in a small cavity in 'hydrocerussite' from a manganese pod at Merehead quarry, Somerset, England. Rumseyite is tetragonal, I4/mmm, a = 4.065(1), c = 12.631(7) Å, V = 208.7(1) Å3, Z = 2. The mineral is translucent pale orange-brown with a white streak and vitreous lustre. It is brittle with perfect {100} cleavage; Dcalc = 7.71 g cm–3 (for the ideal formula, [Pb2OF]Cl). The mean refractive index in air at 589 nm is 2.15. The six strongest reflections in the X-ray powder-diffraction pattern [dmeas in Å, (Irel), (hkl)] are as follows: 2.923(100)(013), 2.875(68)(110), 3.848(41)(011), 6.306(17)(002), 1.680(14)(123), 2.110(12)(006). The crystal structure of rumseyite is based on alternating [OFPb2] and Cl layers. Rumseyite is related to other layered Pb oxyhalides. Fluorine and oxygen are statistically disordered over one crystallographic site. Rumseyite is named in honour of Michael Scott (Mike) Rumsey (1980– ), Curator and Collections Manager at the NHM (London), who discovered the mineral. The mineral and name have been approved by the IMA Commission on New Mineral Names and Classification (IMA 2011-091). The holotype specimen is in the collections of the Natural History Museum, London (specimen number BM1970,110).

The crystal structure of new lead chloride arsenite, Pb5(As3+O3)Cl7 [orthorhombic, Pbcn, a = 16.894(2), b = 10.913 (1), c = 16.760(2) Å, V = 3090.1(7) Å3], from the historic slags of Lavrion, Greece, has been solved by direct methods and refined to R1 = 0.069. The structure contains five symmetrically unique Pb, one As, eight Cl and three O sites. The As atom forms three nearly equal As—O bonds which result in the formation of an AsO3 trigonal pyramid with As at the apex. The Pbl. Pb2, Pb3 and Pb4 atoms are bonded to the AsO3 groups via Pb2+—O bonds to form complex [Pb4(AsO3)] chains parallel to the b axis. The Pb(5) atom is coordinated solely by Cl– anions. The resulting Pb(5)Cl7 polyhedra share common edges and corners to produce bent chains parallel to the c axis. A short compilation of structural features of known lead chloride arsenites is given.

The crystal structure of synthetic ‘plumbonacrite’, Pb5O(OH)2(CO3)3, hexagonal, P63cm, a = 9.0921(7), c = 24.923(3)Å, V = 1784.3(3)Å3, Z = 6, has been solved by direct methods and refined to R = 0.049. There are six symmetrically independent Pb2+ positions in the structure, the coordination polyhedra of which are strongly distorted due to the effect of s2 lone-electron pairs on the Pb2+ cations. The Pb(6) position is disordered with a Pb–Pb distance of 1.24 Å . The structure of ‘plumbonacrite’ is built from complex Pb–O layers parallel to the (001) plane similar to those observed in polymorphs of Pb4(OH)2(SO4)(CO3)2. The structure of these layers can be described in terms of Pb–O,OH motifs and CO3 groups. The smallest structural subunit is the oxocentred [OPb4] tetrahedron that shares three of its Pb-Pb edges with three [(OH)Pb3] distorted triangles to form [O(OH)3Pb7] clusters. These clusters are surrounded by CO3 groups, forming more complex clusters. Due to the disorder in the Pb(6) site, the clusters comprising this site are linked with each other via OH(10) groups to give continuous sheets of Pb–O,OH bonds which are parallel to the (001) plane. The [O(OH)3Pb7] clusters in ‘plumbonacrite’ may be important in more complex Pb carbonate oxo/hydroxo complexes that may exist in aqueous environments.

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.

Yellow needles of 'iodolaurionite', Pb(OH)I, and a novel compound Pb2O(OH)I, have been prepared by hydrothermal reactions of PbO and PbI2 at 170°C. The crystal structure of 'iodolaurionite', Pb(OH)I (orthorhombic, Pnma, a = 7.8244(8), b = 4.2107(4), c = 10.4724(10) Å, V = 345.03(6) Å3, Z = 4) has been refined to R1 = 0.041 for 129 independent observed reflections. The structure is based on the OHPb3 triangles sharing common edges to produce single [OHPb]+ chains extending along the b axis and parallel to the ab plane. The three-dimensional integrity of the structure is provided by the Pb–I bonds and the O–H···I hydrogen bonding. The structure is isotypic with that of laurionite, Pb(OH)Cl. The crystal structure of Pb2O(OH)I (monoclinic, C2/m, a = 13.711(3), b = 4.0975(10), c = 9.584(2) Å, β = 110.64(1)°, V = 503.9(2) Å3, Z = 4), has been solved by direct methods and refined to R1 = 0.053 for 586 independent observed reflections. In the structure of Pb2O(OH)I, O(1)Pb4 tetrahedra link together by sharing edges and corners to form [OPb2]2+ chains similar to those observed in sidpietersite. The O(2) atoms belong to hydroxyl groups attached to both sides of the chains to produce novel [O(OH)Pb2]+ 1D units. The [O(OH)Pb2]+ units are extended parallel to the b axis and lie within the bc plane. The [O(OH)Pb2]+ units are linked together via hydrogen bonding in the (100) plane and by weak Pb–I bonds in the [100] direction. The [O(OH)Pb2]+ bands can be obtained from the [OPb] layer of OPb4 tetrahedra present in the structure of tetragonal PbO (litharge). The continuous [OPb] layer has to be broken into [O2Pb2] bands containing 3- and 4-coordinated O atoms in the 1:1 ratio with subsequent protonation of the 3-coordinated O sites. Relations of Pb(OH)I and Pb2O(OH)I to known Pb hydroxy- and oxyhalides are described briefly.

Rickturnerite, which has the ideal formula Pb7O4[Mg(OH)4](OH)Cl3, is a new mineral from Torr Works (Merehead) quarry, near the village of Cranmore in Somerset, United Kingdom. It occurs as pale emerald green to grey porous aggregates of disordered interwoven minute fibrous crystals with mereheadite, cerussite, calcite, aragonite, mimetite, hydrocerussite, “plumbonacrite” and an uncharacterized lead oxychloride, in cavities inside a manganite and pyrolusite pod. The crystals are typically less than 5 μm wide and 200 μm long, but they can reach 40 × 100 μm in cross-section and over 1 mm in length. The mineral is translucent with a vitreous lustre and each needle is brittle with an indistinct cleavage, breaking with a splintery fracture. The streak is white, the Mohs hardness ∼3 and the density calculated using the empirical formula 6.886 g cm–3. Electron microprobe analyses yielded PbO 87.7, MgO 1.79, CuO 0.14, Cl 6.62 wt.%; H2O was calculated on the basis of structural considerations as 2.27 wt.% totalling 97.02 wt.%. A charge-balanced formula, based on 12 anions, is Pb7.16Mg0.81Cu0.03Cl3.40H4.60O8.60. Rickturnerite is orthorhombic Pnma, with a = 5.8024(6), b = 22.717(2), c = 25.879(3) Å, V = 3411.2(6) Å3 and Z = 8. The diffraction pattern contains strong reflections that define a subcell with a = 5.8034(5), b = 11.3574(9), c = 12.939(2) Å, V = 852.9(6) Å3 (space group Pmm2 which is related to the real unit cell by the transformation matrix [100/020/002]), and weak reflections that correspond to doubled b and c parameters. Since the difference between the large and small cells is only in a number of split and low-occupancy positions in the disordered region of the structure we provide the description of the subcell structure. The five strongest lines in the X-ray powder diffraction pattern [listed as dobs (Å), Iobs, (hkl)] are as follows: 6.474, 100, (400); 3.233, 73, (107); 2.867, 57, (705); 5.636, 44, (011); 3.112, 31, (802). The crystal structure was solved by direct methods and refined using 1318 unique reflections to R1 = 0.063. The structure is composed of a fully ordered part consisting of double [O2Pb3]2+ chains of oxocentred [OPb4] tetrahedra extended along the b-axis, which together with Cl– ions form 2-dimensional blocks parallel to (001). In between these blocks, there is a disordered region containing ordered [Mg(OH)6]4– octahedra and low-occupancy Pb and OH sites with a slight degree of ordering; these produce the weak supercell reflections.

Whiteite-(CaMnMn), CaMnMn2Al2[PO4]4(OH)2·8H2O, is a new hydrous phosphate of Ca, Mn and Al, which is closely related to both jahnsite-(CaMnMn) and the minerals of the whiteite group. It is monoclinic, P2/a, with a = 15.02(2), b = 6.95(1), c =10.13(3) Å, β = 111.6(1)°, V = 983.3(6) Å3, Z = 2 (from powder diffraction data) or a = 15.020(5), b = 6.959(2), c = 10.237(3) Å, β = 111.740(4)°, V = 984.3(5) Å3, Z = 2 (from single-crystal diffraction data). The mineral was found in the Hagendorf Süd granitic pegmatite (Germany) as small (up to 0.5 mm in size) crystals elongated on a and tabular on {010}. The crystals are either simply or polysynthetically twinned on {001}. They crystallize on the walls of voids within altered zwieselite crystals or form coronas (up to 1 mm in diameter) around cubic crystals of uraninite. The mineral is transparent, colourless to pale yellow (depending on Al–Fe3+ substitution), with a vitreous lustre and a white streak. The cleavage is perfect on {001}, the fracture is stepped and the Mohs hardness is 3½. In transmitted light, the mineral is colourless; dispersion was not observed. Whiteite-(CaMnMn) is biaxial (+), α = 1.589(2), β = 1.592(2), γ = 1.601(2) (589 nm), 2Vmeas = 60(10)°, 2Vcalc = 60.3°. The optical orientation is X = b, Z^a = 5°. The calculated and measured densities are Dcalc = 2.768 and Dmeas = 2.70(3) g cm–3, respectively. The mean chemical composition determined by electron microprobe is Na2O 0.53, MgO 0.88, Al2O3 11.66, P2O5 34.58, CaO 4.29, MnO 17.32, FeO 8.32, ZnO 2.60 wt.%, with H2O 19.50 wt.% (determined by the Penfield method), giving a total of 99.68 wt.%. The empirical formula calculated on the basis of four phosphorus atoms per formula unit, with ferric iron calculated to maintain charge balance, is (Ca0.63Zn0.26Na0.14)Σ1.03(Mn0.60Fe0.402+)Σ1.00(Mn1.40Fe0.372+Mg0.18Fe0.063+)Σ2.01(Al1.88Fe0.123+)Σ2.00[PO4]4(OH)2·7.89H2O. The simplified formula is CaMnMn2Al2[PO4]4(OH)2·8H2O. The mineral is easily soluble in 10% HCl at room temperature. The strongest X-ray powder-diffraction lines [listed as d in Å (I) (hkl)] are as follows: 9.443(65)(001), 5.596(25)(011), 4.929(80)(210), 4.719(47)(002), 3.494(46)(400), 2.7958(100)(022). The crystal structure of whiteite-(CaMnMn) was refined for a single crystal twinned on (001) to R1 = 0.068 on the basis of 5702 unique observed reflections. It is similar to the structures of other members of the whiteite group. The mineral is named for the chemical composition, in accordance with whiteite-group nomenclature.

Karpovite, ideally Tl2VO(SO4)2(H2O), was found in a fumarole of the 1st cinder cone of the North Breach of the Great Fissure Tolbachik volcano eruption (1975–1976), Kamchatka Peninsula, Russia. Karpovite occurs as bundles of white, needle-like crystals associated with shcherbinaite, pauflerite, bobjonesite, markhininite, evdokimovite and microcrystalline Mg, Al, Fe and Na sulfates. Karpovite is monoclinic, P21, a = 4.6524(4), b = 11.0757(9), c = 9.3876(7) Å , β = 98.353(2)º, V = 478.60(7) Å3, Z = 2 (from single-crystal diffraction data). The eight strongest lines of the X-ray powder diffraction pattern are (I/d/hkl): 64/4.289/012, 81/4.253/110, 38/3.683/111, 47/3.557/022, 100/3.438/21, 52/2.982/013, 59/2.945/112, 54/2.354/132. The chemical composition determined by the electron microprobe analysis is (wt.%) Tl2O 61.43, VO2 11.53, SO3 23.55, H2O 2.61, total 99.12. The empirical formula (calculated on the basis of 10 O a.p.f.u.) is Tl2.00V0.96S2.03O9(H2O). The simplified formula of karpovite is Tl2VO(SO4)2(H2O), which requires Tl2O 61.93, VO2 12.09, SO3 23.34, H2O 2.62 total 100.00 wt.%. The crystal structure was solved by direct methods and refined to R1 = 0.026 for 4196 independent observed reflections. The structure contains two symmetrically independent Tl+ sites, one V4+ site and two S6+ sites. VO5H2O octahedra and SO4 tetrahedra link together by sharing corners to form kröhnkite-type stripes parallel to the a axis with their planes oriented parallel to (021) and (02). Tl+ cations are located between the chains, linked into a three-dimensional structure. The new mineral is named in honour of Professor Gennadii Alexandrovich Karpov (b. 1938), volcanologist at the Institute of Volcanology, Russian Academy of Sciences, Petropavlovsk-Kamchatskii, Kamchatka Peninsula, Russia.

The crystal structure of mereheadite (monoclinic, Cm, a = 17.372(1), b = 27.9419(19), c = 10.6661(6) Å, β = 93.152(5)°, V = 5169.6(5) Å3) has been solved by direct methods and refined to R1 = 0.058 for 6279 unique observed reflections. The structure consists of alternating Pb–O/OH blocks and Pb–Cl sheets oriented parallel toth e (201) plane and belongs toth e 1:1 type of lead oxide halides with PbO blocks. It contains 30 symmetrically independent Pb positions, 28 of which belong to the PbO blocks, whilst two positions (Pb12 and Pb16) are located within the tetragonal sheets of the Cl– anions. Mereheadite is thus the first naturally occurring lead oxychloride mineral with inter-layer Pb ions. The coordination configurations of the Pb atoms of the PbO blocks are distorted versions of the square antiprism. In one half of the coordination hemisphere, they are coordinated by hard O2– and OH– anions whose number varies from three to four, whereas the other coordination hemisphere invariably consists of four soft Cl– anions located at the vertices of a distorted square. The Pb12 and Pb16 atoms in between the PbO blocks have an almost planar square coordination of four Cl– anions. These PbCl4 squares are complemented by triangular TO3 groups (T = B, C) so that a sevenfold coordination is achieved. The Pb–O/OH block in mereheadite can be obtained from the ideal PbO block by the following list of procedures: (1) removal of some PbO4 groups that results in the formation of square-shaped vacancies; (2) insertion of TO3 groups into these vacancies; (3) removal of some Pb atoms (that correspond to the Pb1A and Pb2A sites), thus transforming coordination of associated O sites from tetrahedral OPb4 tot riangular OHPb3; and (4) replacement of two O2– anions by one OH– anion with twofold coordination; this results in formation of the 1×2 elongated rectangular vacancy. The structural formula that can be derived on the basis of the results of single-crystal structure determination is Pb47O24(OH)13Cl25(BO3)2(CO3). Welch et al. (1998) proposed the formula Pb2O(OH)Cl for mereheadite, which assumes that neither borate nor carbonate is an essential constituent of mereheadite and their presence in the mineral is due to disordered replacements of Cl– anions. However, our study demonstrates that this is not the case, as BO3 and CO3 groups have well-defined structural positions confined in the vacancies of the Pb–O/OH blocks and are therefore essential constituents. Our results also show that mereheadite is not a polymorph of blixite, but is in fact related to symesite. Symesite thus becomes the baseline member of a group of structurallyrelated minerals.

Two new lead oxychloride minerals, hereroite [Pb32(O, ☐)21](AsO4)2((Si,As,V,Mo)O4)2Cl10 and vladkrivovichevite [Pb32O18][Pb4Mn2O]Cl14(BO3)8·2H2O occur in association with asisite, damaraite, kombatite, sahlinite, copper, quartz, barysilite, Mn silicates and a number of Mn oxyhydroxide minerals on a specimen from the Kombat mine in Namibia. The minerals formed as late-stage products of hydrothermal reworking of primary sulfide minerals.

Hereroite is monoclinic, C2/c with a = 23.14(1), b = 22.65(1), c = 12.39(1) Å, β = 102.00(5)°, V = 6351.6(41) Å3 from powder-diffraction data and a = 23.139(4), b = 22.684(4), c = 12.389(2) Å, β = 102.090(3)°, V = 6358.8(18) Å3 from single-crystal data. It is bright orange, with white streak and adamantine lustre. It is brittle with no observed parting or cleavage and has a conchoidal fracture. The calculated density is 8.15 g cm–3. The mean refractive index in air at 589 nm is 2.38. The six strongest reflections in the X-ray powder diffraction pattern [d in Å, (I), (hkl)] are as follows: 2.982(100)(51); 2.795(47)(80); 1.986(24)(8); 1.641(24)(11..); 3.512(23)(61); 3.901(21)(511). Hereroite is named for the Herero people, one of the indigenous tribal groupings in the region where the Kombat mine is located.

Vladkrivovichevite is orthorhombic, Pmmn with a = 12.87(5), b = 27.7(4), c = 11.46(3) Å, V = 4080.1(5) Å3, from powder-diffraction data and a = 12.759(1), b = 27.169(4), c = 11.515(1) Å, V = 3992.0(9) Å3, Z = 2, from single-crystal data. It is pale greenish yellow, with white streak and adamantine lustre. It is brittle with no observed parting or cleavage and has a conchoidal fracture. The calculated density is 7.40 g cm–3. The mean refractive indices in air at 589 nm are 2.30 and 2.34. The six strongest reflections in the X-ray powder diffraction pattern [d in Å, (I), (hkl)] are as follows: 2.860(100)(370); 2.733(84)(073); 3.707(49)(073); 3.068(37)(401); 2.075(32)(473); 1.601(32)(3.14.3). Vladkrivovichevite is named in honour of Prof. Dr Vladimir Gerasimovich Krivovichev (b. 24.04.1946), Head of the Department of Mineralogy, Geological Faculty, St Petersburg State University.

The crystal structures of hereroite and vladkrivovichevite consist of alternating litharge-like O – Pb double layers and chlorine sheets and both are structurally related to other layered lead oxychlorides. In hereroite, tetrahedral AsO4 and (Si, As, V, Mo)O4 groups locate in defects within the O – Pb block, which combines square 'symesite-type' and double-square 'kombatite-type' cavities in its crystal structure. The structure of vladkrivovichevite is based on O – Pb derivative blocks with the interlayer occupied by Cl– anions and oxocentred OPb4Mn2 octahedra whose eight triangular faces are capped by triangular borate anions, BO33–.

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.

The concept of the algorithmic complexity of crystals is developed for a particular class of minerals and inorganic materials based on orthogonal networks, which are defined as networks derived from the primitive cubic net (pcu) by the removal of some vertices and/or edges. Orthogonal networks are an important class of networks that dominate topologies of inorganic oxysalts, framework silicates and aluminosilicate minerals, zeolites and coordination polymers. The growth of periodic orthogonal networks may be modelled using structural automata, which are finite automata with states corresponding to vertex configurations and transition symbols corresponding to the edges linking the respective vertices. The model proposed describes possible relations between theoretical crystallography and theoretical computer science through the theory of networks and the theory of deterministic finite automata.

Evdokimovite, ideally Tl4(VO)3(SO4)5(H2O)5, was found in a fumarole of the 1st cinder cone of the North Breach of the Great Fissure Tolbachik volcano eruption of 1975–1976, Kamchatka Peninsula, Russia. Evdokimovite occurs as thin, colourless needles up to 0.09 mm long associated with shcherbinaite, pauflerite, bobjonesite, markhininite, karpovite and microcrystalline Mg, Al, Fe and Na sulfates. Evdokimovite is monoclinic, P21/n, a = 6.2958(14), b = 10.110(2), c = 39.426(11) Å , β = 90.347(6)º, V = 2509.4(10) Å3 and Z = 4 (from single-crystal diffraction data). The eight strongest lines of the powder X-ray diffraction pattern are (I/d/hkl): 57/9.793/011, 100/8.014/013, 26/6.580/006, 19/ 4.011/026, 29/3.621/118, 44/3.522/125, 19/3.010/036, 21/2.974/212. Chemical composition determined by the electron microprobe analysis is (wt.%): Tl2O 55.40, VO2 14.92, SO3 25.83, H2O 5.75, total 101.90. The empirical formula for evdokimovite calculated on the basis of (Tl + V + S) = 12 a.p.f.u. is Tl4.10V2.83S5.07H10.00O27.94. The simplified formula is Tl4(VO)3(SO4)5(H2O)5. The crystal structure was solved by direct methods and refined to R1 = 0.11 on the basis of 3660 independent observed reflections. V4+O6 octahedra and SO4 tetrahedra share common corners to form two types of vanadyl-sulfate chains, [(VO)(H2O)2(SO4)2]2– and [(VO)2(H2O)3(SO4)3]2–. Thallium atoms are located in between the chains. The structure can be described as a stacking of layers of two types, A and B. The A layer contains [(VO)2(H2O)3(SO4)3]2– chains and the Tl2 and Tl3 atoms, whereas the B layer contains [(VO)(H2O)2(SO4)2]2– chains and the Tl1 atoms. Stacking of the layers can be described as ...A’*BAA’B*A*..., where A and A’ denote A layers with opposite orientations of the [(VO)2(H2O)3(SO4)3]2– chains, and the A* and B* layers are rotated by 180º relative to the A and B layers, respectively. [(VO)2(H2O)3(SO4)3]2– chains are modulated and are arranged to form elliptical tunnels hosting disordered Tl(4), Tl(4A) and Tl(4B) sites. The new mineral is named in honour of Professor Mikhail Dmitrievich Evdokimov (1940–2010), formerly of the Department of Mineralogy, St Petersburg State University, for his contributions to mineralogy and petrology, and especially for teaching mineralogy to several generations of students at the University. Evdokimovite is the most complex V4+ sulfate known to date with structural information amounting to 1130 bits per unit cell, which places evdokimovite among minerals with the complexity of the vesuvianite group.

Oxo-magnesio-hastingsite, ideally NaCa2(Mg2Fe3+3)(Al2Si6)O22O2, is a new anhydrous amphibole from the Deeti volcanic cone in the Gregory rift (northern Tanzania). The mineral occurs as megacrysts up to 12 cm in size in crystal-rich tuff. Oxo-magnesio-hastingsite is brown with a vitreous lustre and has a perfect {110} cleavage. The measured density is 3.19(1) g/cm3. Ferri-kaersutite is biaxial (–), α = 1.706 (2), β = 1.715(2), γ = 1.720(2) (Na light, 589 nm). 2V (calc.) = 73°. Dispersion: r > v, weak; orientation: Y = b; Z ^ c = 8°; pleochroism: strong, Z: dark brown, Y: brown, X: light brown. The average chemical formula of the mineral derived from electron microprobe analyses, Mössbauer spectroscopy and direct water determination is (Na0.67K0.33)Σ1.00(Ca1.87Na0.14Mn0.01)Σ2.02(Mg3.27Fe3+1.25Ti0.44Al0.08)Σ5.04(Al1.80Si6.20O22)(O1.40OH0.60)Σ2.00. It has monoclinic symmetry, space group C2/m and unit-cell parameters a = 9.8837(3), b = 18.0662(6), c = 5.3107(2) Å, b = 105.278(1)o, V = 914.77(5) Å3, Z = 2. The five strongest powder-diffraction lines [d in Å, (I/Io), hkl] are: 3.383 (62) (131), 2.708 (97) (151), 2.555 (100) (), 2.349 (29) () and 2.162 (36) (261). The isotopic composition of H and O, as well as the concentration of trace elements in oxo-magnesio-hastingsite suggest its formation from a melt originated from a mantle source metasomatized by slab-derived fluids.

Detailed analysis of the crystal structures of minerals and inorganic compounds containing oxocentred [OCu4] tetrahedra reveals the following principle for relationships between oxocentred tetrahedra and tetrahedral oxyanions (Tn+O4)−(8−n) with T = S6+ or V5+, or triangular pyramidal oxyanions (SeO3)2− (which may be considered as (SeO3E)2− tetrahedra assuming the lone pair E of selenium to be a fourth ligand): (Tn+O4)−(8−n) tetrahedra are ‘attached’ to the oxocentred tetrahedra so that their grounds (O-O-O and Cu-Cu-Cu) are parallel to each other and the mutual orientation is regular (O corners are exactly under Cu corners). We propose to describe these relationships as ‘face-to-face’, meaning that the oxocentred and cation-centred tetrahedra ‘meet’ along their ‘whole’ triangular faces. Geometric characteristics of ‘face-to-face’ relationships are discussed.