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.

One in four of the Cu-filled cation sites in clinoatacamite, the monoclinic polymorph of atacamite and botallackite, is angle- rather than Jahn-Teller-distorted. Experiments show that this site alone is susceptible to substitution by a non-Jahn-Teller distorting cation of suitable radius and charge, such as Zn2+, and also Ni2+, Co2+, Fe2+, Cd2+ and Mg2+. The crystal symmetry changes to rhombohedral when ∼⅓ of the Cu in this site is substituted by e.g. Zn, thus giving paratacamite; the Zn is essential for stability and forms, with larger proportions of Zn, a series to the end-member in which the site is fully occupied by Zn. This end-member, rhombohedral stoichiometric Cu3Zn(OH)6Cl2, has been characterized using natural specimens from Chile and Iran and is named herbertsmithite. The other cations mentioned behave similarly, producing stabilized rhombohedral paratacamites and end-members analogous to herbertsmithite, which if found in nature, as the Ni analogue has been, should be named species. Clinoatacamite, paratacamite and herbertsmithite have rather similar X-ray powder diffraction patterns, but are readily distinguished by infrared spectroscopy.

Zn-stabilized paratacamite forms blue-green crystals of rhombohedral habit, with vitreous lustre, e = 1.828-1.830, o = 1.835, uniaxial negative, weakly pleochroic O > E, density: 3.75 g cm-3, Mohs hardness: 3-3½; space group R, a = 13.654(5), c = 14.041(6) Å, Z = 24, with pronounced Rm substructure; six strongest XRD lines 5.452 (100), 2.895 (20), 2.760 (74), 2.262 (52), 1.817 (18), 1.708 (21).

Herbertsmithite forms dark green crystals of rhombohedral habit, with vitreous lustre, e = 1.817, o = 1.825, uniaxial negative, weakly pleochroic O > E, density: 3.95 g cm-3, Mohs hardness: 3-3½;; space group Rm with no superstructure observed, a = 6.834(1), c = 14.075(2) Å, Z = 3; six strongest XRD lines 5.466 (55), 4.702 (14), 2.764 (100), 2.266 (36), 1.820 (13), 1.709 (18).