The new mineral pohlite (IMA2022–043), Pb7(IO3)(OH)4Cl9, was found at La Compania mine, Sierra Gorda, Antofagasta Province, Antofagasta, Chile, where it occurs in cavities in an oxidised portion of a quartz vein in association with massive aragonite and anhydrite. Pohlite crystals are transparent, colourless to pale grey blades, up to 4 mm in length. The mineral has a white streak, adamantine lustre and is nonfluorescent. It is brittle with irregular, conchoidal fracture. The Mohs hardness is ~2½ and it has no cleavage. The calculated density is 5.838(2) g cm–3. Optically, the mineral is biaxial (+) with α < 2.01(est.), β = 2.02 (calc.), γ = 2.05 (calc.); 2V = 60(5)°; moderate r > v dispersion; orientation: Y ∧ a ≈ 20°, Z ∧ b ≈ 30°; and is nonpleochroic. The Raman spectrum exhibits bands consistent with IO3– and O–H. Electron microprobe analysis provided the empirical formula Pb6.74I1.00Cl9.29O6.71H4.23. The five strongest powder X-ray diffraction lines are [dobs Å(I)(hkl)]: 3.818(91)(023, 122, 1$\bar{2}$1), 3.674(85)($\bar{1}\bar{2}$1, $\bar{1}$22, 200, 104), 3.399(47)($\bar{2}$10, 210, $\bar{1}$04), 2.378(100)(302, 041, $\bar{2}$24) and 1.9943(45)(multiple). Pohlite is triclinic, P$\bar{1}$, a = 7.3366(5), b = 9.5130(9), c = 16.2434(15) Å, α = 81.592(7), β = 84.955(7), γ = 89.565(6)°, V = 1117.13(17) Å3 and Z = 2. The structure of pohlite (R1 = 0.0328 for 3394 I > 2σI) contains two types of clusters, a [Pb4(OH)3]5+ cluster formed by short Pb–O bonds and a [Pb3(OH)(IO3)]28+ ‘double cluster’ formed by short I–O bonds and short- to medium-length Pb–O bonds. Long Pb–Cl and I–Cl bonds link the clusters together in three dimensions.

The new mineral tombstoneite (IMA2021-053), (Ca0.5Pb0.5)Pb3Cu2+6Te6+2O6(Te4+O3)6(Se4+O3)2(SO4)2⋅3H2O, occurs at the Grand Central mine in the Tombstone district, Cochise County, Arizona, USA, in cavities in quartz matrix in association with jarosite and rodalquilarite. Tombstoneite crystals are green pseudohexagonal tablets, up to 100 μm across and 20 μm thick. The mineral has a pale green streak and adamantine lustre. It is brittle with irregular fracture and a Mohs hardness of ~2½. It has one perfect cleavage on {001}. The calculated density is 5.680 g cm–3. Optically, the mineral is uniaxial (–) and exhibits pleochroism: O = green, E = light yellow green; O > E. The Raman spectrum exhibits bands consistent with Te6+O6, Te4+O3, Se4+O3 and SO4. Electron microprobe analysis provided the empirical formula (Ca0.51Pb0.49)Σ1.00Pb3.00Cu2+5.85Te6+2.00O6(Te4+1.00O3)6(Se4+0.69Te4+0.24S0.07O3)2(S1.00O4)2⋅3H2O. Tombstoneite is trigonal, P321, a = 9.1377(9), c = 12.2797(9) Å, V = 887.96(18) Å3 and Z = 1. The structure of tombstoneite (R1 = 0.0432 for 1205 I > 2σI) contains thick heteropolyhedral layers comprising Te6+O6 octahedra, Jahn-Teller distorted Cu2+O5 pyramids, Te4+O3 pyramids and Se4+O3 pyramids. Pb2+ cations without stereoactive 6s2 lone-pair electrons are hosted in pockets in the heteropolyhedral layer. Pb2+ cations, possibly with stereoactive 6s2 lone-pair electrons, are located in the interlayer region along with SO4 tetrahedra and H2O groups. Within the heteropolyhedral layer, the Te6+O6 octahedra and the Te4+O3 pyramids form finite Te6+O3(Te4+O3)3 clusters with a pinwheel-like configuration. This is the first known finite complex including both Te4+ and Te6+ polyhedra in any natural or synthetic tellurium oxysalt structure.

Lead-containing (Pb-B-X)-2H apatites encompass a number of [AF]4[AT]6[(BO4)6]X2 compounds used for waste stabilization, environmental catalysis and ion conduction, but the influence of the stereochemically active lone-pair electrons of Pb2+ on crystal chemistry and functionality is poorly understood. This article presents a compilation of existing structural data for Pb apatites that demonstrate paired electrons of Pb2+ at both the AF and AT results in substantial adjustments to the PbFO6 metaprism twist angle, φ. New structure refinements are presented for several natural varieties as a function of temperature by single-crystal X-ray diffraction (XRD) of vanadinite-2H (ideally Pb10(VO4)6Cl2), pyromorphite-2H (Pb10(PO4)6Cl2), mimetite-2H/M (Pb10(As5+O4)6Cl2) and finnemanite-2H (Pb10(As3+O3)6Cl2). A supercell for mimetite is confirmed using synchrotron single-crystal XRD. It is suggested the superstructure is necessary to accommodate displacement of the stereochemically active 6s2 lone-pair electrons on the Pb2+ that occupy a volume similar to an O2− anion. We propose that depending on the temperature and concentration of minor substitutional ions, the mimetite superstructure is a structural adaptation common to all Pb-containing apatites and by extension apatite electrolytes, where oxide ion interstitials are found at similar positions to the lonepair electrons. It is also shown that plumbous apatite framework flexes substantially through adjustments of the PbFO6 metaprism twist-angles (φ) as the temperature changes. Finally, crystalchemical [100] zoning observed at submicron scales will probably impact on the treatment of diffraction data and may account for certain inconsistencies in reported structures.