‘Mineral evolution’ has attracted much attention in the last decade as a counterpart of the long-established biological concept, but is there a corresponding ‘mineral extinction’? We present new geochronological data from uranium-bearing secondary minerals and show that they are relatively recent, irrespective of the age of their primary uranium sources. The secondary species that make up much of the diversity of minerals appear to be ephemeral, and many may have vanished from the geological record without trace. Nevertheless, an ‘extinct’ mineral species can recur when physiochemical conditions are appropriate. This reversibility of ‘extinction’ highlights the limitations of the ‘evolution’ analogy. Mineral occurrence may be time-dependent but does not show the unique contingency between precursor and successor species that is characteristic of biological evolution.

Mineral species should be identified by an end-member formula and by using the dominant-valency rule as recommended by the IMA–CNMNC. However, the dominant-end-member approach has also been used in the literature. These two approaches generally converge, but for some intermediate compositions, significant differences between the dominant-valency rule and the dominant end-member approach can be observed. As demonstrated for garnet-supergroup minerals, for example, the end-member approach is ambiguous, as end-member proportions strongly depend on the calculation sequence. For this reason, the IMA–CNMNC strongly recommends the use of the dominant-valency rule for mineral nomenclature, because it alone may lead to unambiguous mineral identification. Although the simple application of the dominant-valency rule is successful for the identification of many mineral compositions, sometimes it leads to unbalanced end-member formulae, due to the occurrence of a coupled heterovalent substitution at two sites along with a heterovalent substitution at a single site. In these cases, it may be useful to use the site-total-charge approach to identify the dominant root-charge arrangement on which to apply the dominant-constituent rule. The dominant-valency rule and the site-total-charge approach may be considered two procedures complementary to each other for mineral identification. Their critical point is to find the most appropriate root-charge and atomic arrangements consistent with the overriding condition dictated by the end-member formula. These procedures were approved by the IMA−CNMNC in May 2019.

The new mineral anatolyite Na6(Ca,Na)(Mg,Fe3+)3Al(AsO4)6 was found in the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. It is associated with potassic feldspar, hematite, tenorite, cassiterite, johillerite, tilasite, ericlaxmanite, lammerite, arsmirandite, sylvite, halite, aphthitalite, langbeinite, anhydrite, wulffite, krasheninnikovite, fluoborite, pseudobrookite and fluorophlogopite. Anatolyite occurs as aggregates (up to 2 mm across) of rhombohedral–prismatic, equant or slightly elongated along [001] crystals up to 0.2 mm. The mineral is transparent, pale brownish–pinkish, with vitreous lustre. It is brittle, cleavage was not observed and the fracture is uneven. The Mohs’ hardness is ca 4½. Dcalc is 3.872 g cm–3. Anatolyite is optically uniaxial (–), ω = 1.703(4) and ε = 1.675(3). Chemical composition (wt.%, electron microprobe) is: Na2O 16.55, K2O 0.43, CaO 2.49, MgO 5.80, MnO 0.16, CuO 0.69, ZnO 0.55, Al2O3 5.01, Fe2O3 7.94, TiO2 0.18, SnO2 0.17, SiO2 0.04, P2O5 0.55, As2O5 60.75, SO3 0.03, total 101.34. The empirical formula based on 24 O apfu is (Na5.90K0.10)Σ6.00(Ca0.50Na0.13Zn0.08Mn0.03)Σ0.74(Mg1.63Fe3+1.12Al0.15Cu0.10)Σ3.00(Al0.96Ti0.03Sn0.01)Σ1.00(As5.97P0.09Si0.01)Σ6.07O24. Anatolyite is trigonal, R$\bar{3}$c, a = 13.6574(10), c = 18.2349(17) Å, V = 2945.6(4) Å3 and Z = 6. The strongest reflections of the powder XRD pattern [d,Å(I)(hkl)] are: 7.21(33)(012), 4.539(16)(113), 4.347(27)(211), 3.421(20)(220), 3.196(31)(214), 2.981(17)(223), 2.827(100)(125) and 2.589(18)(410). The crystal structure was solved from single-crystal XRD data to R = 4.77%. The structure is based on a 3D heteropolyhedral framework formed by M4O18 clusters [M1 = Al and M2 = (Mg,Fe3+)] linked with AsO4 tetrahedra. (Ca,Na) and Na cations centre A1O6 and A2O8 polyhedra in voids of the framework. Anatolyite is isostructural with yurmarinite. The new mineral is named in honour of the outstanding Russian crystallographer, mineralogist and mathematician Anatoly Kapitonovich Boldyrev (1883–1946).

Molybdenite from two porphyry copper mineralisation sites within the South Urals was studied by electron microprobe (EMPA), micro x-ray diffraction (μXRD) and electron backscattered diffraction (EBSD) methods. Elevated contents of rhenium (0.2 to 0.4, sometimes up to 1.1 wt.%) form linear zones from several to tens of micrometres wide and up to hundreds of micrometres long parallel to the elongation of molybdenite flakes. In most cases Re-rich zones are composed of the rhombohedral (3R) polytype of molybdenite, while the rest of the molybdenite flakes with ca. 0.1 wt.% of Re consist of hexagonal (2H) molybdenite. In rare cases Re-rich zones are confined to grain boundaries of molybdenite-2H. It is shown that both μXRD and EBSD are the most appropriate tools to distinguish different polytypes within a single grain of molybdenite.

A new phyllosilicate mineral, lipuite (IMA2014-085), has been discovered from the N'Chwaning III mine, Kalahari Manganese Fields, Northern Cape Province, Republic of South Africa. It occurs as platy, tabular, or granular crystals and veined agglomerate in association with Mn-bearing sugilite, taniajacoite, pectolite, richterite, norrishite and namansilite. Lipuite is dark red–brown with vitreous lustre, red streak, an estimated Mohs hardness of 5 and the measured density is 2.83(3) g/cm3. It is biaxial (+) and characterised by bright red to dark red colour in thin section with measured refractive indices in white light: α = 1.635(1), β = 1.653(1), γ = 1.670(1) and 2V = 86(2)°. The Raman spectra of lipuite are composed of over 21 bands at 109, 146, 162, 183, 206, 244, 288, 342, 362, 455, 496, 520, 552, 613, 669, 886, 930, 971, 1097, 3487 and 3540 cm–1. The empirical formula from microprobe analyses is (based on total number of cations = 27.5 and structural refinement): K1.12Na8.16(Mn4.77Fe0.07)Σ4.84Mg0.44[Si11.97O30(OH)4](PO4)0.94O2(OH)2·4H2O. The idealised formula is: KNa8Mn3+5Mg0.5[Si12O30(OH)4](PO4)O2(OH)2·4H2O.

Lipuite is orthorhombic, space group Pnnm, a = 9.080(3), b = 12.222(3), c = 17.093(5) Å, V = 1897.0(9) Å3 and Z = 2. The strongest powder X-ray diffraction peaks [d, Å (I) (hkl)] are: 9.965(40)(011), 2.938(33)(310), 2.895(100)(311), 2.777(38)(224), 2.713(53)(320), 2.483(32)(126), 2.086(35)(046) and 1.534(40)(446). The crystal structure of lipuite is characterised by sheets of SiO4 tetrahedra that are linked together along [010] by K+, Na+, Mn3+, Mg2+ and P5+ cations, as well as hydrogen bonds. These tetrahedral sheets consist of 14-membered rings of SiO4 tetrahedra that zigzag along [100]. The two independent Mn3+ cations are both octahedrally coordinated. They form five-membered, edge-shared octahedral clusters between the SiO4 tetrahedral sheets. Lipuite represents a rather unique structure type and its silicate tetrahedral sheets can be considered a derivative of the silicate sheets in mica.

The new minerals camanchacaite, NaCaMg2[AsO4]2[AsO3(OH)2], chinchorroite, Na2Mg5(As2O7)2(AsO3OH)2(H2O)10, espadaite, Na4Ca3Mg2[AsO3(OH)]2[AsO2(OH)2]10(H2O)6·H2O, magnesiofluckite, CaMg(AsO3OH)2(H2O)2, picaite, NaCa[AsO3OH][AsO2(OH)2] and ríosecoite, Ca2Mg(AsO3OH)3(H2O)2, were discovered on two closely related specimens collected from the Torrecillas mine, Iquique Province, Chile. These minerals occur as secondary phases on massive quartz–hematite also in association with anhydrite, gypsum, halite and talmessite. Camanchacaite is monoclinic, C2/c, a = 12.470(9), b = 12.554(9), c = 6.848(9) Å, β = 113.75(2)°, V = 981.3(16) Å3 and Z = 4. It has a protonated alluaudite-type structure. Chinchorroite is triclinic, P$\bar{1}$, a = 8.7777(2), b = 8.8570(3), c = 9.7981(7) Å, α = 91.097(6), β = 110.544(8), γ = 103.167(7)°, V = 690.43(7) Å3 and Z = 1. The structure contains abbreviated chains of five edge-sharing Mg octahedra that are linked by pyroarsenate and hydrogen-arsenate groups. Espadaite is orthorhombic, Ccca, a = 12.3649(10), b = 22.181(2), c = 18.3292(13) Å, V = 5027.1(7) Å3 and Z = 4. The structure is based on heteropolyhedral sheets of formula {Ca3Mg2[AsO3(OH)]2[AsO2(OH)2]10}4− that contain large voids; NaO6 polyhedra occupy the interlayer region. Magnesiofluckite is triclinic, P$\bar{1}$, a = 8.4143(6), b = 7.5321(5), c = 6.8917(4) Å, α = 82.477(6), β = 97.682(6), γ = 95.379(6)°, V = 427.84(5) Å3 and Z = 2. It is isostructural with fluckite. Picaite is monoclinic, P21/c, a = 7.2474(4), b = 14.6547(7), c = 7.2624(5) Å, β = 99.520(7)°, V = 760.70(8) Å3 and Z = 4. The structure contains chains of edge-sharing Na− and Ca octahedra with bridging AsO3(OH) and AsO2(OH)2 tetrahedra. Ríosecoite is triclinic, P$\bar{1}$, a = 6.8110(9), b = 7.3156(12), c = 11.7773(17) Å, α = 83.466(6), β = 84.394(6), γ = 79.779(6)°, V = 571.95(15) Å3 and Z = 2. The structure contains tetramers of edge-sharing CaO7 and CaO8 polyhedra linked by MgO6 octahedra and bridging AsO3(OH) groups to form chains.

We present here new data on the low-sulfide mineralisation in the upper endocontact of the Noril'sk 1 intrusion. Twenty four mineral species of platinum-group elements and their solid solutions, as well as numerous unnamed phases, including an Sb analogue of vincentite, As and Sn analogues of mertieite-I and a Sn analogue of mertieite-II have been found. It is shown that the features of the mineral association: (1) the atypical trend of TiO2 and Fe2+ in chromian spinel; (2) the composition of the Pt–Fe alloys with a Fe/Fe + Pt range of 0.26–0.37 (logfO2 ≈ – (9–10); and (3) crystallisation of high-temperature sperrylite from silicate melt (at >800°C and logfS2 < –10.5), which is possible under fO2 of FMQ to FMQ-2 in mafic magma, are due to the reducing conditions of their formation and evolution. Droplet-like inclusions of silicate-oxide minerals in сhromian spinels and sulfides in platinum-group minerals are interpreted to be trapped droplets of co-existing sulfide melt. The captured sulfide melt has evolved in the direction of increasing the fugacity of sulfur: troilite + pentlandite (Fe>Ni) – in sperrylite (paragenesis I) to monoclinic pyrrhotite + pentlandite (Ni≈Fe) + chalcopyrite – in Pt–Fe alloys (paragenesis II). Paragenesis from the sulfide aggregates in the silicate matrix are more fractionated: pyrrhotite + pyrrhotite (Ni>Fe) + chalcopyrite (III) and pyrite + pentlandite (Ni>>Fe) + millerite (IV). Pd arsenides and antimonides crystallised later than sperrylite and isoferroplatinum, as a result of the evolution of a sulfide melt with an increased activity of the element ligands (Te, Sn, Sb and As).

We describe the new species ognitite, NiBiTe, and a Co-rich variety of maucherite, hitherto unreported; both were discovered in the Ognit ultramafic complex of Neoproterozoic age in Eastern Sayans, Russia. The mean composition of ognitite (n = 7) is: Ni 17.05, Fe 0.07, Cu 0.14, Pd 0.14, Te 32.53, Bi 49.64, total 99.57 wt.%, corresponding to: (Ni1.11Cu0.008Fe0.005Pd0.005)Σ1.13Bi0.90Te0.97 (Σ atoms = 3 apfu). Ognitite is trigonal, space group P3m1 [R1 = 0.0276 for 81 reflections with Fo > 4σ(Fo)]. The unit-cell parameters derived from the single-crystal X-ray diffraction data are: a = 3.928(1) Å, c = 5.385(1) Å and V = 71.95(4) Å3, with Z = 1. The c:a ratio is 1.37. The powder X-ray diffraction data obtained on the same fragment used for the single-crystal study are: a = 3.9332(4) Å, c = 5.3920(6) Å and V = 72.24(1) Å3. Ognitite exhibits the brucite-type structure with edge-sharing NiTe3Bi3 octahedra forming sheets parallel to (0001). It is related to melonite, but is distinct compositionally by the extreme Bi-enrichment (melonite and its synthetic analogue contain <0.4 Bi apfu), and structurally as Bi and Te are ordered at two distinct sites, leading to the loss of the centre of symmetry in ognitite.

At more than 9 wt.% Co, or ~2 apfu Co, the core of Co-rich maucherite [(Ni,Co)11As8] in a zoned crystal, which is surrounded by Co-depleted orcelite, far surpasses the norm (≤1 and up to 3.9 wt.% Co). The unit-cell parameters of the Co-rich maucherite are: a = 6.85(2) and c = 21.83(5) Å, which are based on results of synchrotron micro-Laue diffraction.

The host rock consists of serpentine, clinochlore (Mg# 95–97) and skeletal chromite. We favour the metastable crystallisation of fluid-saturated globules of a sulfide–arsenide melt to explain the anomalous compositions of ore minerals at Ognit. These anomalies seem consistent with rapid cooling in a fluid-enriched system, possibly related to late-stage degassing of the magma, as reflected in a prominent metasomatic aureole at the contact with the enclosing gneissic rocks.

X-ray laboratory diffraction contrast tomography (LabDCT) produces three-dimensional (3D) maps of crystallographic orientation. The non-destructive nature of the technique affords the key benefit of full 3D context of these, and other, in situ measurements. This study is the first to apply the technique to any material other than a metal or silicon. We report the first 3D measurements of the crystallographic orientation of olivine, which also makes this study the first to apply LabDCT to (1) a non-metallic, non-cubic system and (2) geological material. First, we scanned fragments of olivine set in resin alongside glass microbeads using LabDCT and absorption contrast tomography (ACT). Then we reconstructed these data assuming an orthorhombic crystal system. We show that: (1) the regions within the sample that index well according to the orthorhombic system correspond to olivine fragments in the ACT image; (2) crystalline regions not corresponding to olivine are not indexed assuming the same lattice parameters; and (3) the diffraction data discriminates crystalline from non-crystalline materials as expected. Finally, we demonstrate that the method resolves sub-degree orientation differences between distinct regions within individual olivine fragments. We conclude that DCT can be applied to the study of rocks and other crystalline materials, and offers advantages over conventional techniques. We also note that LabDCT may offer a solution to the crystallographic measurement of substances that would otherwise be difficult to measure due to challenges in obtaining a perfect sample polish. Future developments to accommodate larger experimental volumes and additional crystallographic systems within a sample promises to expand the applicability and impact of DCT.

Levantite, with the end-member formula KCa3(Al2Si3)O11(PO4), is the phosphate analogue of latiumite, KCa3(Al3Si2)O11(SO4, CO3) found in gehlenite–wollastonite hornfels on Har Parsa, Negev Desert, Israel. Levantite forms later zones on long-prismatic crystals of latiumite. Rarer homogeneous colourless levantite crystals up to 0.2 mm long and with mean composition (K0.94Ba0.01Na0.01□0.04)Σ1.00(Ca2.96Mg0.03)Σ2.99{(Si2.69Al2.06Fe3+0.16P0.06)Σ4.97O11}[(PO4)0.65(SO4)0.35]Σ1.00 were noted. Minerals of the levantite–latiumite series are associated with gehlenite, wollastonite, clinopyroxene of the esseneite–diopside series, anorthite and Ti-bearing andradite. Levantite crystalises in space group P21 with unit-cell parameters a = 12.1006(9) Å, b = 5.1103(4) Å, c = 10.8252(9) Å, β = 107.237(8)°, V = 639.34(9) Å3 and Z = 2. The structure of levantite is analogous to latiumite. It is formed by tetrahedral hybrid zweier double layers [(Si,Al)10O22] connected by Ca atoms. Three Ca atoms linked to different double layers are bridged over by (PO4) and minor (SO4) groups. K atoms reside in the cavities between two superimposed zweier double layers. The measured micro-indentation hardness of levantite gave VHN50 = 580(19) (mean of 14), range 550–611 kg/mm2, which correlates with 5 on the Mohs scale. Cleavage is good on (100). Twinning on (100) is polysynthetic or simple. The calculated density is 2.957 g cm–3. Levantite is optically negative with α = 1.608(2), β = 1.618(2), γ = 1.622(2) (λ = 589 nm), 2Vmeas. = 70(5)° and 2Vcalc. = 64.3°. Dispersion of the optical axes r > v is weak; the optical orientation is: Z = b, X ^ c = 22–27°; and it is non-pleochroic. Minerals of the levantite–latiumite series from Israel show characteristic Raman spectra with the main bands at 994 cm–1 [ν1(SO4)2–] and 945 cm–1 [ν1(PO4)3–]. The band intensity ν1(PO4)3–/ν1(SO4) ratio is well correlated with P and S contents in the investigated minerals. The strongest lines in the powder diffraction pattern [dobs, Å (I, %) (hkl)] are: 3.0762(100)(310), 2.8551(96)($\bar 2$13), 2.9704(92)($\bar 3$12), 2.8573(83)(013), 2.5552(66)(020), 2.8228(48)(212), 2.8893(40)(400), and 3.0634(30)(103).

Three samples of halurgite were re-examined: two from the Chelkar salt dome in the North Caspian Region, Western Kazakhstan (the type locality and including the type specimen), and one from a new locality in the Satimola salt dome located in the same region. The crystal structure of halurgite has been solved for the first time on the specimen from Chelkar with the empirical formula Mg3.94[B8.03O13.03(OH)1.97]2·7.16H2O; refinement began with single-crystal X-ray diffraction data and was subsequently refined on a powder sample using the Rietveld method (Rp = 0.0232, Rwp = 0.0354 and Robs = 0.0558). The idealised crystal chemical formula of halurgite is Mg4[B8O13(OH)2]2·7H2O. The mineral is monoclinic, P2/c, a = 13.201(2), b = 7.5622(10), c = 13.185(2) Å, β = 91.834(14)°, V = 1315.6(4) Å3 and Z = 2. The crystal structure is unique. Eight B polyhedra form a fundamental building block [B8O16(OH)2], which is a six-membered borate ring (built by two pairs of B tetrahedra and two B triangles) with two additional triangular BO2(OH) groups. Each [B8O16(OH)2] ring is linked to six adjacent analogous rings to form a [B8O13(OH)2]∞ layer. These layers are connected via MgO6 and Mg(OH)2(H2O)4 octahedra into a microporous heteropolyhedral pseudo-framework. The crystal structure of halurgite can also be described in terms of an approach developed for heterophyllosilicates containing three-layer HOH modules, where HOH refers to an octahedral layer O sandwiched between two heteropolyhedral layers H. In halurgite the HOH module consists of two heteropolyhedral (BO3 triangles + BO4 tetrahedra) borate H layers [B8O13(OH)2]∞ and a central interrupted O layer composed of MgO6 octahedra, whereas a more voluminous Mg(OH)2(H2O)4 octahedral complex and additional H2O molecules are located between HOH modules. Halurgite and four related synthetic H-free borates M2Cd3B16O28 and M2Ca3B16O28 (M = Rb or Cs) can be considered microporous heterophylloborates.

Hitachiite, Pb5Bi2Te2S6, is a new mineral discovered in the Hitachi mine, located in the Ibaraki Prefecture of Japan. The mean of 21 electron microprobe analyses gave: Pb 52.01, Bi 23.06, Fe 0.69, Sb 0.17, Te 13.74, S 9.71, Se 0.54, total 100.04 wt.%. The empirical chemical formula based on 15 apfu is (Pb4.75Fe0.23)Σ4.98(Bi2.09Sb0.03)Σ2.12Te2.04(S5.73Se0.13)Σ5.86, ideally Pb5Bi2Te2S6. Synchrotron single-crystal X-ray diffraction experiments indicated that hitachiite has trigonal symmetry, space group P${\bar 3}$m1, with a = 4.2200(13) Å, c = 27.02(4) Å and Z = 1. The four strongest diffraction peaks shown in the powder X-ray pattern [d, Å (I)(hkl)] are: 3.541(35)(012), 3.391(59)(013), 3.039(100)(015) and 2.114(56)(110). The calculated density (Dcalc) for the empirical chemical formula is 7.54 g/cm3.

The crystal structure of hitachiite has been refined using synchrotron single-crystal X-ray diffraction data, to R = 7.38% and is based on ABC-type stacking of 15 layers (five Pb, two Bi, two Te, and six S layers) along the [001] direction, and with each layer ideally containing only one kind of atom. The stacking sequence is described as Te–Bi–S–Pb–S–Pb–S–Pb–S–Pb–S–Pb–S–Bi–Te. The discovery of hitachiite implies that the minerals of the Bi2Te2S–PbS join might form a homologous series of Bi2Te2S·nPbS.

The new minerals cuatrocapaite-(NH4) (IMA2018-083) and cuatrocapaite-(K) (IMA2018-084) are the NH4- and K-dominant members of a series with the general formula (NH4,K)3(NaMg□)(As2O3)6Cl6·16H2O. Both minerals were found at the Torrecillas mine, Iquique Province, Chile, where they occur as secondary alteration phases. Both minerals occur as hexagonal tablets up to ~0.3 mm in diameter. They are transparent, with a vitreous lustre and white streak. For both, the Mohs hardness is ca. 2½, the crystals are somewhat flexible, but not elastic, the fracture is irregular and the cleavage is perfect on {001}. The measured densities are 2.65(2) and 2.76(2) g/cm3 for the NH4- and K-dominant species, respectively. Optically, cuatrocapaite-(NH4) is uniaxial (–) with ω = 1.779(3) and ε = 1.541(3) and cuatrocapaite-(K) is uniaxial (–) with ω = 1.777(3) and ε = 1.539(3) (white light). The minerals are insoluble in acids, but decompose in NaOH(aq). The empirical formulas, determined from electron-microprobe analyses, are (NH4)2.48Na1.66Mg0.87K0.09(As12O18.05)Cl5.88·16.02H2O and K2.68Na1.33Mg0.93(NH4)0.31(As12O18.01)Cl6.16·16.04H2O. The minerals are trigonal, space group R${\bar 3}$m; the cuatrocapaite-(NH4) cell parameters are a = 5.25321(19), c = 46.6882(19) Å, V = 1115.80(9) Å3 and Z = 1; the cuatrocapaite-(K) cell parameters are a = 5.2637(15), c = 46.228(8) Å, V = 1109.2(7) Å3 and Z = 1. The structures, refined for cuatrocapaite-(NH4) to R1 = 1.78% for 544 Io > 2σI reflections, contain four types of layers: (1) a planar neutral As2O3 (arsenite) sheet; (2) an (${\rm NH}_{\rm 4}^{\vskip -2pt\rm \scale65% +} $,K+) layer that links adjacent arsenite sheets; (3) a Cl– layer placed on the As side of each arsenite; and (4) a layer containing partially occupied Na, Mg and H2O sites that is flanked on either side by Cl layers. The layer sequence for the type 1, 2 and 3 layers is identical to the Cl–As2O3–K–As2O3–Cl layer sequence in the structures of lucabindiite and gajardoite.

Dokuchaevite, ideally Cu8O2(VO4)3Cl3, was found in the Yadovitaya fumarole of the Second scoria cone of the North Breach of the Great Tolbachik Fissure Eruption (1975–1976), Tolbachik volcano, Kamchatka Peninsula, Russia. Dokuchaevite occurs on the crusts of various copper sulfate exhalative minerals (such as kamchatkite and euchlorine) as individual prismatic crystals. Dokuchaevite is triclinic, P$\bar{1}$, a = 6.332(3), b = 8.204(4), c = 15.562(8) Å, α = 90.498(8), β = 97.173(7), γ = 90.896(13)°, V = 801.9(7) Å3 and R1 = 0.057. The eight strongest lines of the X-ray powder diffraction pattern are (d, Å (I)(hkl): (15.4396)(18)(00$\bar{1}$), (7.2762)(27)(0$\bar{1}$1), (5.5957)(43)(012), (4.8571)(33)($\bar{1}\bar{1}$1), (3.1929) (29)(023), (2.7915)(30)(202), (2.5645)(21)(032), (2.5220)(100)(1$\bar{3}$0), (2.4906)(18)(130) and (2.3267)(71)(2$\bar{2}$2). The chemical composition determined by electron-microprobe analysis is (wt.%): CuO 60.87, ZnO 0.50, FeO 0.36, V2O5 19.85, As2O5 6.96, SO3 0.44, MoO3 1.41, SiO2 0.20, P2O5 0.22, Cl 10.66, –O = Cl2 2.41, total 99.06. The empirical formula calculated on the basis of 17 anions per formula unit is (Cu7.72Zn0.06Fe0.05)Σ7.83(V2.20As0.61Mo0.10S0.06P0.03Si0.03)Σ3.03O13.96Cl3.04.

The crystal structure of dokuchaevite represents a new structure type with eight Cu sites, which demonstrate the remarkable diversity of Cu2+ mixed-ligand coordination environments. The crystal structure of dokuchaevite is based on OCu4 tetrahedra that share common corners thus forming [O2Cu6]8+ single chains. Two of the eight symmetrically independent copper atoms do not form Cu–O bonds with additional oxygen atoms, and thus are not part of the OCu4 tetrahedra, but provide the three-dimensional integrity of the [O2Cu6]8+ chains into a framework. TO4 mixed tetrahedral groups are located within the cavities of the framework. The structural formula of dokuchaevite can be represented as Cu2[Cu6O2](VO4)3Cl3.